WO2015080189A1 - Radical polymerization initiator and method for producing polymers - Google Patents
Radical polymerization initiator and method for producing polymers Download PDFInfo
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- WO2015080189A1 WO2015080189A1 PCT/JP2014/081334 JP2014081334W WO2015080189A1 WO 2015080189 A1 WO2015080189 A1 WO 2015080189A1 JP 2014081334 W JP2014081334 W JP 2014081334W WO 2015080189 A1 WO2015080189 A1 WO 2015080189A1
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- substituent
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- polymer
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- 229920000642 polymer Polymers 0.000 title claims abstract description 66
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- 239000007870 radical polymerization initiator Substances 0.000 title claims abstract description 29
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 24
- 150000003498 tellurium compounds Chemical class 0.000 claims abstract description 22
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 15
- 125000001424 substituent group Chemical group 0.000 claims description 64
- 238000006116 polymerization reaction Methods 0.000 claims description 63
- -1 ditelluride compound Chemical class 0.000 claims description 46
- 239000000178 monomer Substances 0.000 claims description 39
- 125000003118 aryl group Chemical group 0.000 claims description 37
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 29
- 125000004432 carbon atom Chemical group C* 0.000 claims description 24
- 125000005843 halogen group Chemical group 0.000 claims description 21
- 125000001931 aliphatic group Chemical group 0.000 claims description 18
- 125000003368 amide group Chemical group 0.000 claims description 15
- 238000010526 radical polymerization reaction Methods 0.000 claims description 12
- 125000003107 substituted aryl group Chemical group 0.000 claims description 12
- 125000005346 substituted cycloalkyl group Chemical group 0.000 claims description 12
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 239000003999 initiator Substances 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 102
- 239000000243 solution Substances 0.000 description 48
- 238000004458 analytical method Methods 0.000 description 36
- 238000005160 1H NMR spectroscopy Methods 0.000 description 30
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 28
- 238000003756 stirring Methods 0.000 description 26
- 239000007789 gas Substances 0.000 description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 22
- 238000005227 gel permeation chromatography Methods 0.000 description 22
- 239000004793 Polystyrene Substances 0.000 description 21
- 229920002223 polystyrene Polymers 0.000 description 21
- 238000004587 chromatography analysis Methods 0.000 description 20
- 239000000725 suspension Substances 0.000 description 19
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 19
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- 229910052714 tellurium Inorganic materials 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 17
- 150000003254 radicals Chemical class 0.000 description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 14
- 229920005604 random copolymer Polymers 0.000 description 13
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 12
- LCMDQKIQBKULEI-UHFFFAOYSA-N dimethyl ditelluride Chemical compound C[Te][Te]C LCMDQKIQBKULEI-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 125000000753 cycloalkyl group Chemical group 0.000 description 11
- JPIIVHIVGGOMMV-UHFFFAOYSA-N ditellurium Chemical compound [Te]=[Te] JPIIVHIVGGOMMV-UHFFFAOYSA-N 0.000 description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 9
- 239000012044 organic layer Substances 0.000 description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 8
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 8
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 8
- 239000002954 polymerization reaction product Substances 0.000 description 8
- 239000012264 purified product Substances 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- CFEMBVVZPUEPPP-UHFFFAOYSA-N 2-methylbuta-1,3-diene;prop-2-enenitrile Chemical compound C=CC#N.CC(=C)C=C CFEMBVVZPUEPPP-UHFFFAOYSA-N 0.000 description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- WIYVVIUBKNTNKG-UHFFFAOYSA-N 6,7-dimethoxy-3,4-dihydronaphthalene-2-carboxylic acid Chemical compound C1CC(C(O)=O)=CC2=C1C=C(OC)C(OC)=C2 WIYVVIUBKNTNKG-UHFFFAOYSA-N 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 125000001309 chloro group Chemical group Cl* 0.000 description 5
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 4
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 4
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 4
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- SFLRURCEBYIKSS-UHFFFAOYSA-N n-butyl-2-[[1-(butylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound CCCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCCC SFLRURCEBYIKSS-UHFFFAOYSA-N 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- BIXCBWDGHACUIH-UHFFFAOYSA-N 1-(butylditellanyl)butane Chemical compound CCCC[Te][Te]CCCC BIXCBWDGHACUIH-UHFFFAOYSA-N 0.000 description 3
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- PMJHHCWVYXUKFD-PLNGDYQASA-N (3z)-penta-1,3-diene Chemical compound C\C=C/C=C PMJHHCWVYXUKFD-PLNGDYQASA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
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- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 2
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- CYTJMBLSQUBVMS-UHFFFAOYSA-N n-[[2-cyanopropan-2-yl(formyl)amino]hydrazinylidene]formamide Chemical compound N#CC(C)(C)N(C=O)NN=NC=O CYTJMBLSQUBVMS-UHFFFAOYSA-N 0.000 description 2
- WMRNGPYHLQSTDL-UHFFFAOYSA-N n-cyclohexyl-2-[[1-(cyclohexylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound C1CCCCC1NC(=O)C(C)(C)N=NC(C)(C)C(=O)NC1CCCCC1 WMRNGPYHLQSTDL-UHFFFAOYSA-N 0.000 description 2
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- 125000000962 organic group Chemical group 0.000 description 2
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 2
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 2
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- 229910052717 sulfur Inorganic materials 0.000 description 2
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- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- AJURYMCOXVKKFB-UHFFFAOYSA-M trimethyl(3-prop-2-enoyloxypropyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCOC(=O)C=C AJURYMCOXVKKFB-UHFFFAOYSA-M 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C395/00—Compounds containing tellurium
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/06—Hydrocarbons
- C08F12/08—Styrene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
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- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/08—Isoprene
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- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with nitriles
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
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- C08F4/00—Polymerisation catalysts
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/04—Azo-compounds
Definitions
- the present invention relates to a radical polymerization initiator useful for producing a polymer having a double bond at a molecular end, and a method for producing a polymer using the radical polymerization initiator.
- Patent Document 1 discloses a method for producing a polymer having a branched structure in which a macromonomer having a group having a polymerizable carbon-carbon double bond at the molecular end is polymerized.
- a vinyl monomer is polymerized by an atom transfer radical polymerization method using a polymerization initiator (such as an organic halide) and a catalyst (such as a transition metal complex), and a terminal is formed with a halogen.
- a polymerization initiator such as an organic halide
- a catalyst such as a transition metal complex
- the atom transfer radical polymerization method using allyl halide as a polymerization initiator has limitations on the types of vinyl monomers that can be applied, and depending on the type of vinyl monomer, it may be difficult to control the polymerization reaction. There is a problem that it does not progress. Therefore, a radical polymerization initiator having a carbon-carbon double bond that can be applied to a wide variety of radical polymerizable monomers such as vinyl monomers and perform a controlled polymerization reaction is eagerly desired.
- radical polymerization initiators are reactive with carbon-carbon double bonds, many radical polymerization initiators have sufficient polymerization activity when carbon-carbon double bonds are introduced into the molecule. There is a problem that it cannot be shown, and a radical polymerization initiator having a carbon-carbon double bond as desired has not been obtained.
- organic tellurium compounds as disclosed in Patent Document 2 and Patent Document 3 are known as radical polymerization initiators capable of radical polymerization of vinyl monomers and the like by controlling molecular weight distribution and the like.
- JP 2007-254758 A (US2006 / 0052563A) WO2004 / 014962 pamphlet (US2006 / 0167199A) JP 2007-277533 A
- the present invention has been made in view of the above-described prior art, and can be applied to a wide variety of radical polymerizable monomers to perform a controlled polymerization reaction, and has a double bond at the molecular end. It is an object of the present invention to provide a radical polymerization initiator useful for producing a polymer, and a method for producing a polymer using the radical polymerization initiator.
- the present inventors diligently studied a radical polymerization initiator used for a living radical polymerization reaction.
- the living radical polymerization reaction of the radical polymerizable monomer is performed in the presence of a radical polymerization initiator composed of an organic tellurium compound having at least one non-aromatic carbon-carbon double bond at the ⁇ -position.
- a radical polymerization initiator composed of an organic tellurium compound having at least one non-aromatic carbon-carbon double bond at the ⁇ -position.
- the following radical polymerization initiator [1], the following [2], [3], [4], [5] polymer production method and the following [6] polymer are provided. Is done.
- a radical polymerization initiator comprising an organic tellurium compound represented by the following formula (1).
- R 1 represents an alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group and an optionally substituted aromatic heterocyclic group.
- R 2 and R 3 each independently represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group which may have a substituent, or an aromatic which may have a substituent.
- R 7 represents an alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, and an optionally substituted aromatic heterocyclic group.
- R 8 and R 9 each independently represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group that may have a substituent, or an aromatic that may have a substituent.
- [2] A method for producing a polymer, comprising radically polymerizing a radical polymerizable monomer in the presence of the radical polymerization initiator according to [1].
- [3] The method for producing a polymer as described in [2], wherein an azo radical generator is further present in the polymerization reaction system.
- [4] The method for producing a polymer as described in [2] or [3], wherein the polymerization reaction system is radically polymerized with a radical polymerizable monomer while irradiating light.
- [5] The method for producing a polymer as described in any one of [2] to [4], wherein a ditelluride compound represented by the following formula (3) is further present in the polymerization reaction system.
- R 10 and R 11 each independently have an alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group and a substituent; Represents a group selected from aromatic heterocyclic groups which may be [6]
- a radical polymerization initiator useful for the production of a polymer having a double bond at the molecular end, which can be applied to a wide variety of radical polymerizable monomers to perform a controlled polymerization reaction. And a method for producing a polymer using the radical polymerization initiator.
- “Having a double bond at the molecular end” means the formula: (R 5 ) (R 6 ) C ⁇ C (R 4 ) —C (R 2 ) () derived from the organic tellurium compound represented by the formula (1)
- the group represented by R 3 ) — constitutes one terminal of the polymer chain.
- Radical polymerization initiator The radical polymerization initiator of the present invention is composed of an organic tellurium compound represented by the formula (1).
- R 1 represents an alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, and an optionally substituted aromatic complex.
- the group selected from a cyclic group is represented.
- R 1 is preferably an alkyl group or an aryl group which may have a substituent.
- “optionally substituted” means “unsubstituted or substituted”.
- the number of carbon atoms of the alkyl group of R 1 is not particularly limited, but is preferably 1 to 10, more preferably 1 to 8, and further preferably 1 to 5 from the viewpoint of availability.
- the alkyl group for R 1 include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n -Straight chain alkyl groups such as decyl group; branched alkyl groups such as isopropyl group, sec-butyl group and tert-butyl group.
- the carbon number of the cycloalkyl group of the cycloalkyl group which may have a substituent for R 1 is usually 3 to 10, preferably 3 to 8, and more preferably 5 or 6, from the viewpoint of availability. preferable.
- Examples of the cycloalkyl group of the cycloalkyl group which may have a substituent for R 1 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like.
- the substituent of the cycloalkyl group that may have the substituent of R 1 is not particularly limited as long as it does not hinder the polymerization reaction.
- halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom
- hydroxyl group alkyl group having 1 to 8 carbon atoms such as methyl group, ethyl group, n-propyl group and isopropyl group; methoxy group, ethoxy group and the like
- the carbon number of the aryl group of the aryl group which may have a substituent of R 1 is usually 6 to 20, preferably 6 to 15 and more preferably 6 to 10 from the viewpoint of availability.
- Examples of the aryl group of the aryl group which may have a substituent include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and an anthranyl group.
- the substituent of the aryl group that may have a substituent is not particularly limited as long as it does not interfere with the polymerization reaction. For example, the thing similar to what was shown as a substituent of the cycloalkyl group which may have a substituent is mentioned.
- the aromatic heterocyclic group of the aromatic heterocyclic group which may have a substituent for R 1 usually has 1 to 15 carbon atoms, and preferably 3 to 15 from the viewpoint of availability. 10 is more preferable.
- the aromatic heterocyclic group of the aromatic heterocyclic group which may have a substituent is a 5-membered aromatic heterocyclic ring such as a pyrrolyl group, an imidazolyl group, a furyl group, a thienyl group, an oxazolyl group or a thiazolyl group.
- 6-membered aromatic heterocyclic groups such as pyridyl group, pyrimidyl group, pyridazyl group and pyrazinyl group; condensed aromatic heterocyclic groups such as benzimidazolyl group, quinolyl group and benzofuranyl group;
- the substituent of the aromatic heterocyclic group which may have a substituent is not particularly limited as long as it does not interfere with the polymerization reaction. For example, the thing similar to what was shown as a substituent of the cycloalkyl group which may have a substituent is mentioned.
- R 2 and R 3 each independently represent a hydrogen atom, an aliphatic hydrocarbon group, an aryl group that may have a substituent, or an aromatic complex that may have a substituent.
- R 2 and R 3 a hydrogen atom or an aliphatic hydrocarbon group is preferable.
- the carbon number of the aliphatic hydrocarbon group for R 2 and R 3 is preferably 1 to 10, more preferably 1 to 8, and further preferably 1 to 5.
- Examples of the aliphatic hydrocarbon group for R 2 and R 3 include an alkyl group having 1 to 10 carbon atoms such as a methyl group and an ethyl group; an alkenyl group having 2 to 10 carbon atoms such as a 1-propenyl group and a 2-propenyl group; Alkynyl groups having 2 to 10 carbon atoms such as 1-propynyl group and 2-propynyl group: cycloalkyl groups having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group;
- aryl group which may have a substituent for R 2 and R 3 include the same aryl groups as those which may have a substituent for R 1 .
- aromatic heterocyclic group which may have a substituent of R 2 and R 3 are the same as those shown as the aromatic heterocyclic group which may have a substituent of R 1 . Things.
- the halogen atom for R 2 and R 3 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- the carbon number of the hydrocarbyloxycarbonyl group of R 2 and R 3 is preferably 2 to 10, more preferably 2 to 8, and further preferably 2 to 5.
- the hydrocarbyloxycarbonyl group for R 2 and R 3 include alkyloxycarbonyl groups such as methyloxycarbonyl group and ethyloxycarbonyl group; alkenyloxycarbonyl groups such as ethenyloxycarbonyl group and 2-propenyloxycarbonyl group; propargyl Alkynyloxycarbonyl group such as oxycarbonyl group; having a substituent such as phenoxycarbonyl group, 4-methylphenyloxycarbonyl group, 4-chlorophenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group Aryloxycarbonyl group which may be present; and the like.
- group (X represented by -C (X) -N (r 1 ) (r 2) represents an oxygen atom, a sulfur atom, a selenium atom, r 1, r 2 independently represents a hydrogen atom or an organic group having 1 to 10 carbon atoms.
- group represented by the formula: —SO 2 —N (r 1 ) (r 2 ) (r 1 , r 2 is Or a group represented by the formula: —N (r 1 ) —C (O) — (r 2 ) (where r 1 and r 2 have the same meaning as described above).
- group (X represented by -C (X) -N (r 1 ) (r 2) represents an oxygen atom, a sulfur atom, a selenium atom, r 1, r 2 independently represents a hydrogen atom or an organic group having 1 to 10 carbon atoms.)
- Examples of the organic group for r 1 and r 2 include straight or branched alkyl groups having 1 to 10 carbon atoms such as methyl and ethyl groups; straight chain having 2 to 10 carbon atoms such as 1-propenyl group and 2-propenyl group.
- Examples of the group represented by the formula: —C (X) —N (r 1 ) (r 2 ) include aminocarbonyl group, methylaminocarbonyl group, ethylaminocarbonyl group, benzylaminocarbonyl group, phenylaminocarbonyl group, dimethylamino Examples include carbonyl group, phenylmethylaminocarbonyl group, dimethylaminothiocarbonyl group, dimethylaminoselenocarbonyl group and the like.
- Examples of the group represented by the formula: —SO 2 —N (r 1 ) (r 2 ) include an aminosulfonyl group, a methylaminosulfonyl group, a benzylaminosulfonyl group, and a dimethylaminosulfonyl group.
- Examples of the group represented by the formula: —N (r 1 ) —C (O) — (r 2 ) include an acetylamino group and a benzoylamino group.
- R 4 , R 5 and R 6 each independently have a hydrogen atom, an aliphatic hydrocarbon group, an aryl group which may have a substituent, or a substituent.
- R 4 , R 5 and R 6 a hydrogen atom, an aliphatic hydrocarbon group (including a ring formed by combining R 4 and R 5 ), a hydrocarbyloxycarbonyl group or the above formula (2 ) Is preferred.
- Specific examples of the aliphatic hydrocarbon group for R 4 , R 5 and R 6 include the same as those shown as the aliphatic hydrocarbon group for R 2 and R 3 .
- Specific examples of the aryl group which may have a substituent for R 4 , R 5 and R 6 include the same aryl groups as those which may have a substituent for R 1. It is done.
- Specific examples of the aromatic heterocyclic group which may have a substituent of R 4 , R 5 and R 6 include those shown as the aromatic heterocyclic group which may have a substituent of R 1 The same thing is mentioned.
- Specific examples of the halogen atom for R 4 , R 5 and R 6 include the same as those shown for the halogen atom for R 2 and R 3 .
- hydrocarbyloxycarbonyl group for R 4 , R 5 and R 6 include the same as those shown as the hydrocarbyloxycarbonyl group for R 2 and R 3 .
- Specific examples of the amide group for R 4 , R 5 and R 6 include the same amide groups as those for R 2 and R 3 .
- R 7 represents an alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, and an optionally substituted aromatic group. Represents a group selected from a heterocyclic group; Among these, as R 7 , an alkyl group or an aryl group which may have a substituent is preferable.
- alkyl group of R 7 an optionally substituted cycloalkyl group, an optionally substituted aryl group, and an optionally substituted aromatic heterocyclic group are each an alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, or an optionally substituted aromatic heterocyclic group of R 1. The thing similar to what was shown as is mentioned.
- R 8 and R 9 are each independently a hydrogen atom, an aliphatic hydrocarbon group, an aryl group which may have a substituent, or an aromatic complex which may have a substituent.
- R 8 and R 9 a hydrogen atom or an aliphatic hydrocarbon group is preferable.
- R 8 and R 9 aliphatic hydrocarbon groups, aryl groups optionally having substituents, aromatic heterocyclic groups optionally having substituents, halogen atoms, hydrocarbyloxycarbonyl groups, amide groups
- Specific examples include an aliphatic hydrocarbon group represented by R 2 and R 3, an aryl group which may have a substituent, an aromatic heterocyclic group which may have a substituent, a halogen atom, and a hydrocarbyl, respectively. The thing similar to what was shown as an oxycarbonyl group and an amide group is mentioned.
- R 2 to R 6 two groups selected from these may be bonded to form a ring other than an aromatic ring.
- a hydrocarbon ring is preferable.
- the ring is preferably a 5- to 7-membered ring, more preferably a 6-membered ring.
- the ring may have a cyclopentene ring which may have a substituent, or a substituent.
- the ring When the ring does not have a double bond like the bond of R 5 and R 6 , the ring may be a cyclopentane ring which may have a substituent or a cyclohexane ring which may have a substituent. And a cycloheptane ring which may have a substituent. Examples of the substituent bonded to the ring are the same as those shown as the substituents for R 2 to R 6 .
- organic tellurium compound represented by the formula (1) examples include 3-methylterranyl-1-propene, 3-methylterranyl-2-methyl-1-propene, 3-methylterranyl-2-phenyl-1-propene, 3- Methyl terranyl-3-methyl-1-propene, 3-methyl terranyl-3-phenyl-1-propene, 3-methyl terranyl-3-cyclohexyl-1-propene, 3-methyl terranyl-3-cyano-1-propene, 3-ethyl terranyl- 1-propene, 3-methylteranyl-3-dimethylaminocarbonyl-1-propene, 3-[(n-propyl) terranyl] -1-propene, 3-isopropylterranyl-1-propene, 3- (n-butyl) Terranylpropene, 3-[(n-hexyl) terranyl] -1-propene, 3-phenylterran
- Examples of the organic tellurium compound represented by the formula (1) include a compound represented by the following formula (4), a compound represented by the following formula (5), and a metal tellurium according to the method described in the pamphlet of WO2004 / 014963. Can be obtained by reacting.
- R 2 to R 6 represent the same as described above.
- X represents a halogen atom.
- the halogen atom represented by X may be any of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, but is preferably a chlorine atom or a bromine atom.
- R 1 represents the same as described above.
- M represents an alkali metal such as lithium, sodium or potassium; an alkaline earth metal such as magnesium or calcium; or copper.
- M is an alkali metal
- m is 1, when M is an alkaline earth metal, m is 2, and when M is copper, m is 1 or 2.
- M when M is magnesium, one of the two groups represented by R 1 may be a halogen atom. That is, the compound represented by the formula (5) may be a so-called Grignard reagent.
- metal tellurium is suspended in a solvent under an inert gas atmosphere to prepare a suspension, and a compound represented by the formula (5) is added to the suspension to perform a reaction.
- an organic tellurium compound represented by the formula (1) can be obtained by adding a compound represented by the formula (4) to the obtained reaction solution and further performing a reaction.
- the amount of the compound represented by the formula (5) to be used is usually 0.5 to 1.5 mol, preferably 0.8 to 1.2 mol, relative to 1 mol of metal tellurium.
- the amount of the compound represented by the formula (4) to be used is usually 0.5 to 1.5 mol, preferably 0.8 to 1.2 mol, relative to 1 mol of metal tellurium.
- Examples of the inert gas include nitrogen gas, helium gas, and argon gas.
- Examples of the solvent to be used include ether solvents such as diethyl ether and tetrahydrofuran; amide solvents such as dimethylformamide; aromatic solvents such as toluene; aliphatic hydrocarbon solvents such as hexane;
- ether solvents such as diethyl ether and tetrahydrofuran
- amide solvents such as dimethylformamide
- aromatic solvents such as toluene
- aliphatic hydrocarbon solvents such as hexane
- R 2 to R 9 are the same as those described above, provided that R 4 , R 5 and R 6 are not groups represented by the formula (2).
- X 1 and X 2 are halogen atoms. (Preferably represents a chlorine atom or a bromine atom.) It can obtain by performing the same reaction using the compound shown by these.
- the amount of the compounds represented by the formulas (4a) to (4c) is usually 0.25 to 0.00 per mol of metal tellurium. 75 mol, preferably 0.4 to 0.6 mol.
- the amount of the compound represented by formula (5) is usually 0.5 to 1.5 mol, preferably 0.8 to 1.2 mol, relative to 1 mol of metal tellurium.
- the target product can be isolated by a known post-treatment operation and separation / purification means.
- the reaction solution is washed successively with degassed water, degassed ammonium chloride aqueous solution, and degassed saturated saline, and then the organic layer is dried and concentrated to obtain a crude product.
- the target organic tellurium compound can be obtained by high purity by refine
- the organic tellurium compound represented by the formula (1) used as the radical polymerization initiator of the present invention has at least one non-aromatic carbon-carbon double bond at the ⁇ position with respect to Te.
- the carbon-carbon double bond is introduced at the polymerization initiation terminal, A living radical polymerization reaction excellent in controllability can be performed. Therefore, a polymer having a double bond at the molecular end can be efficiently produced by using the radical polymerization initiator of the present invention.
- the polymer production method of the present invention is characterized by radical polymerization of a radical polymerizable monomer in the presence of the radical polymerization initiator of the present invention.
- the radical polymerizable monomer used in the present invention is not particularly limited as long as it is capable of radical polymerization.
- Styrene ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-methoxystyrene, 4-tert-butylstyrene, 4-n-butylstyrene, 4-tert-butoxystyrene, 2- Styrene such as hydroxymethylstyrene, 2-chlorostyrene, 4-chlorostyrene, 2,4-dichlorostyrene, 1-vinylnaphthalene, divinylbenzene, 4-styrenesulfonic acid or alkali metal salts thereof (sodium salt, potassium salt, etc.) System monomers; ⁇ -olefin monomers such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-decene;
- Unsaturated carboxylic monomers such as maleic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, maleic anhydride; Conjugated diene monomers such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1,3-pentadiene; And non-conjugated diene monomers such as 4-methyl-1,4-hexadiene and 7-methyl-1,6-octadiene.
- radical polymerizable monomers can be used singly or in combination of two or more.
- the production method of the polymer of the present invention is a broader variety of radically polymerizable monomers than atom transfer radical polymerization using allyl halide as a polymerization initiator, which is a conventional method for introducing a carbon-carbon double bond at the polymerization initiation terminal.
- the polymer can perform a controlled polymerization reaction. Therefore, the method for producing a polymer of the present invention can be particularly suitably used when a radical polymerizable monomer that is difficult to perform a controlled polymerization reaction by a conventional method is used.
- the radically polymerizable monomer particularly preferably used in the method for producing a polymer of the present invention is a (meth) acrylic acid ester having a functional group selected from a hydroxyl group, an amino group and an ammonium group, At least one radical polymerizable monomer selected from (meth) acrylic acids, (meth) acrylamides, ⁇ -olefins, vinyl monomers having a vinyl group that is not conjugated to an aromatic ring, and conjugated diene monomers. It includes a mer.
- the amount of the organic tellurium compound represented by the formula (1) and the radical polymerizable monomer used may be appropriately adjusted in consideration of the molecular weight and molecular weight distribution of the target polymer.
- the amount of the organic tellurium compound represented by the formula (1) is 0.00005 to 0.2 mol, preferably 0.0001 to 0.02 mol with respect to 1 mol of the radical polymerizable monomer.
- radical polymerization for example, an organic tellurium compound represented by the formula (1), a radical polymerizable monomer, and, if necessary, a solvent in a container substituted with an inert gas such as nitrogen gas, helium gas or argon gas. Can be added and stirred at a predetermined temperature for a predetermined time.
- an inert gas such as nitrogen gas, helium gas or argon gas.
- a solvent generally used in radical polymerization reaction can be used.
- aromatic hydrocarbons such as benzene and toluene; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate; ethers such as dioxane and tetrahydrofuran (THF); N, N-dimethylformamide (DMF) and the like Amides; sulfur-containing compounds such as dimethyl sulfoxide (DMSO); alcohols such as methanol, ethanol, isopropanol and n-butanol; halogen-containing compounds such as chloroform, carbon tetrachloride and trifluoromethylbenzene; ethyl cellosolve and butyl cellosolve And cellosolves such as 1-methoxy-2-propanol; water; and the like.
- aromatic hydrocarbons such as benzene and toluene
- ketones such as acetone and methyl
- solvents can be used singly or in combination of two or more.
- the amount used is, for example, 0.01 to 50 ml, preferably 0.05 to 10 ml, more preferably 0.1 to 5 ml with respect to 1 g of the radical polymerizable monomer.
- reaction temperature and reaction time suitably. Usually, it is 20 to 150 ° C. for 1 minute to 100 hours, preferably 40 to 100 ° C. for 0.1 to 30 hours.
- the reaction is usually performed under normal pressure, but may be performed under pressure or under reduced pressure.
- an azo radical generator may be further present in the polymerization reaction system.
- the polymerization reaction is further promoted, and the polymer can be obtained efficiently.
- the azo radical generator can be used without particular limitation as long as it is an azo radical generator used as a polymerization initiator or polymerization accelerator in ordinary radical polymerization.
- AIBN 2,2′-azobis (isobutyronitrile)
- AMBN 2,2′-azobis (2-methylbutyronitrile)
- ADVN 2,2′-azobis (2,4-dimethylvaleronitrile)
- ACVA 4,4′-azobis (4-cyanovaleric acid )
- 1,1′-azobis (1-acetoxy-1-phenylethane 2,2′-azobis (2-methylbutyramide), 2,2′-azobis (4-methoxy-2,4) -Dimethylvaleronitrile
- 2,2'-azobis 2,2'-azobis (2-methylamidinopropane) dihydrochloride, 2,2'-azobis [
- azo radical generators are preferably selected as appropriate according to the reaction conditions.
- a low temperature 40 ° C. or lower
- 2,2′-azobis (2,4-dimethylvaleronitrile) ADVN
- 2,2′-azobis (4-methoxy-2,4-dimethyl) Valeronitrile) is preferred
- an intermediate temperature 40 to 80 ° C.
- 2,2′-azobis (isobutyronitrile) AIBN
- 2,2′-azobis (2-methylbutyronitrile) ) AMBN
- dimethyl-2,2′-azobisisobutyrate MAIB
- 1,1′-azobis (1-acetoxy-1-phenylethane 1,1′-azobis (1-acetoxy-1-phenylethane
- 1,1′-azobis cyclohexane-1-carbonitrile
- 2-cyano-2-propylazoformamide 2,2′-azobis (N-butyl-2-methylpropylene) N'amido)
- 2,2'-azobis N- cyclohexyl-2-methylpropionamide
- 2,2'-azobis 2,4,4-trimethylpentane
- the amount used is, for example, 0.01 to 100 mol, preferably 0.05 to 10 mol, more preferably 0. 0 mol with respect to 1 mol of the organic tellurium compound represented by the formula (1). 05 to 2 mol.
- the polymerization reaction may be performed while irradiating the polymerization reaction system with light.
- the irradiation light is preferably ultraviolet light (light having a wavelength of 200 to 380 nm) or visible light (light having a wavelength of 380 to 830 nm).
- the light irradiation can be carried out by a method usually used in a photopolymerization reaction.
- Light may be irradiated using a light source such as a xenon lamp, a krypton lamp, or an LED lamp.
- a light source such as a xenon lamp, a krypton lamp, or an LED lamp.
- the use of an azo radical generator and the irradiation of light can be used in combination, but usually the polymerization reaction is sufficiently accelerated if either one is performed.
- a ditelluride compound represented by the formula (3) may further be present in the polymerization reaction system.
- the polymerization reaction is better controlled, and a polymer having a molecular weight closer to the theoretical value and a narrow molecular weight distribution can be obtained. .
- R 10 and R 11 each independently have an alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group and a substituent.
- Specific examples of the alkyl group of R 10 and R 11, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, and an aromatic heterocyclic group which may have a substituent Examples include an alkyl group represented by R 1 , an optionally substituted cycloalkyl group, an optionally substituted aryl group, and an optionally substituted aromatic heterocyclic ring. The thing similar to what was shown as a group is mentioned.
- ditelluride compound represented by the formula (3) examples include dimethylditelluride, diethylditelluride, di (n-propyl) ditelluride, diisopropylditelluride, dicyclopropylditelluride, di (n-butyl).
- Ditelluride di (sec-butyl) ditelluride, di (tert-butyl) ditelluride, dicyclobutylditelluride, diphenylditelluride, bis (p-methoxyphenyl) ditelluride, bis (p-aminophenyl) ditelluride, bis (P-nitrophenyl) ditelluride, bis (p-cyanophenyl) ditelluride, bis (p-sulfonylphenyl) ditelluride, bis (2-naphthyl) ditelluride, 4,4′-dipyridylditelluride and the like can be mentioned.
- These ditelluride compounds can be used individually by 1 type or in combination of 2 or more types.
- the amount used is, for example, 0.01 to 100 mol, preferably 0.1 to 10 mol, based on 1 mol of the organic tellurium compound represented by the formula (1).
- the amount is preferably 0.1 to 5 mol.
- the use of the ditelluride compound represented by the formula (3) can be used in combination with the use of an azo radical generator and the irradiation with light.
- the polymer After completion of the reaction, the polymer can be isolated and purified according to a conventional method. For example, a method of isolating a polymer by distilling off a solvent or remaining radical polymerizable monomer in a reaction solution under reduced pressure, or a method of precipitating a polymer by pouring the reaction solution into a poor solvent Is mentioned.
- the molecular weight of the polymer obtained by the method for producing a polymer of the present invention can be adjusted by the reaction time and the amount of the organic tellurium compound.
- the number average molecular weight is 500 to 1,000,000, preferably 1 , 50,000 to 50,000.
- the molecular weight distribution (Mw / Mn) is usually 1.01 to 2.50, preferably 1.01 to 2.00, more preferably 1.01 to 1.50, and still more preferably 1.01 to 1. 30, most preferably 1.01-1.15.
- a copolymer in the method for producing a polymer of the present invention, can be obtained by using two or more radically polymerizable monomers.
- a random copolymer can be obtained by allowing two or more kinds of radically polymerizable monomers to simultaneously exist in the polymerization reaction system.
- a block copolymer can be obtained by sequentially reacting two or more kinds of radically polymerizable monomers. Can be obtained.
- the growth terminal of the polymer chain during the polymerization reaction is a highly reactive organic tellurium moiety (R 1 -Te- or R 7 -Te-) derived from the radical polymerization initiator of the present invention. And has a living property.
- the growth terminal of the polymer chain having the living property is exposed to the air, the growth terminal is replaced with a hydrogen atom or a hydroxyl group, and the growth terminal is deactivated.
- the method for producing a polymer of the present invention it is possible to efficiently obtain a polymer having a double bond at a molecular end and having a controlled molecular weight or molecular weight distribution, which is useful as a macromonomer or the like. .
- Example 1 Under a nitrogen atmosphere, in a 300 mL three-necked flask, 11.48 g (90 mmol) of metal tellurium was suspended in 86 ml of THF. The resulting suspension was cooled to 0 ° C. with stirring. While continuing to stir and cool the suspension, 86.0 ml (94.5 mmol) of methyllithium (1.10 M diethyl ether solution) was added dropwise to the suspension over 10 minutes. After completion of dropping, the contents in the three-necked flask were stirred at room temperature (25 ° C.) for 20 minutes to obtain a reaction solution in which metal tellurium completely disappeared. The resulting reaction solution was cooled to 0 ° C. with stirring.
- Example 2 Under a nitrogen atmosphere, 6.38 g (50 mmol) of metal tellurium was suspended in 50 ml of THF in a 300 mL three-necked flask. The resulting suspension was cooled to 0 ° C. with stirring. While continuing to stir and cool the suspension, 48.6 ml (52.5 mmol) of phenyllithium (1.08 M cyclohexane / diethyl ether solution, manufactured by Kanto Chemical Co., Inc.) was dropped into the suspension over 10 minutes. . After completion of dropping, the contents in the three-necked flask were stirred at room temperature (25 ° C.) for 20 minutes to obtain a reaction solution in which metal tellurium completely disappeared.
- the resulting reaction solution was cooled to 0 ° C. with stirring. While continuing stirring and cooling of the reaction solution, 6.35 g (52.5 mmol) of allyl bromide was added to the reaction solution. The reaction was continued by stirring the contents in the three-necked flask for 2 hours, and the reaction solution was returned to room temperature. The resulting reaction solution was washed successively with degassed water, degassed saturated NH 4 Cl aqueous solution, and degassed saturated NaCl aqueous solution. Subsequently, anhydrous magnesium sulfate was added to the organic layer (washed reaction solution), dried, and then filtered through Celite in a nitrogen atmosphere.
- Example 3 Under a nitrogen atmosphere, 3.76 g (29.5 mmol) of metal tellurium was suspended in 38 ml of THF in a 300 mL three-necked flask. The resulting suspension was cooled to 0 ° C. with stirring. While continuing to stir and cool the suspension, 19.4 ml (31.0 mmol) of n-butyllithium (1.6M hexane solution) was added dropwise to the suspension over 10 minutes. After completion of dropping, the contents in the three-necked flask were stirred at room temperature (25 ° C.) for 20 minutes to obtain a reaction solution in which metal tellurium completely disappeared. The resulting reaction solution was cooled to 0 ° C. with stirring.
- Example 4 Under a nitrogen atmosphere, 3.39 g (26.6 mmol) of metal tellurium was suspended in 25 ml of THF in a 300 mL three-necked flask. The resulting suspension was cooled to 0 ° C. with stirring. While continuing to stir and cool the suspension, 25.1 ml (27.9 mmol) of methyllithium (1.11 M diethyl ether solution) was added dropwise to the suspension over 10 minutes. After completion of dropping, the contents in the three-necked flask were stirred at room temperature (25 ° C.) for 20 minutes to obtain a reaction solution in which metal tellurium completely disappeared. The resulting reaction solution was cooled to 0 ° C. with stirring.
- Example 5 In a nitrogen-substituted glove box, 0.68 g (10 mmol) of isoprene (manufactured by Tokyo Chemical Industry Co., Ltd., the same shall apply hereinafter), 0.53 g of acrylonitrile (manufactured by Wako Pure Chemical Industries, Ltd., the same shall apply hereinafter) 10 mmol), 36.7 mg (0.20 mmol) of 3-methylterranyl-1-propene obtained in Example 1, 5.7 mg (0.02 mmol) of dimethylditelluride obtained in Synthesis Example 1, and 1,1′-azobis (Cyclohexane-1-carbonitrile) (manufactured by Wako Pure Chemical Industries, Ltd., the same shall apply hereinafter) 24.4 mg (0.10 mmol), and an internal standard for gas chromatographic analysis (hereinafter referred to as “internal standard”), 0.24 g was added (manufactured by Kojun Pharmaceutical Co., Ltd., the same applies hereinafter), and
- the obtained polymerization reaction product was purified by distilling off volatile components under reduced pressure, and the purified product was dried to obtain an isoprene-acrylonitrile random copolymer.
- the conversion rate of isoprene was 93%
- the conversion rate of acrylonitrile was 84%.
- GPC analysis based on polystyrene standard sample
- the weight average molecular weight (Mw) was 7,060
- the number average molecular weight (Mn) was 6,130
- the molecular weight distribution (Mw / Mn) was 1.15.
- 1 H-NMR analysis it had a double bond at the terminal at a rate of 98%.
- Example 6 No 1,1′-azobis (cyclohexane-1-carbonitrile) was added, and during the polymerization reaction, the polymerization reaction system was irradiated with light using a 6 W output LED lamp (using a 5% ND filter). Except for the above, a polymerization reaction was carried out in the same manner as in Example 5 to obtain an isoprene-acrylonitrile random copolymer. As a result of gas chromatographic analysis, the conversion rate of isoprene was 88%, and the conversion rate of acrylonitrile was 81%. As a result of GPC analysis (polystyrene standard sample reference), Mw was 6,730, Mn was 6,100, and Mw / Mn was 1.09. As a result of 1 H-NMR analysis, it had double bonds at the terminals at a ratio of 96%.
- Example 7 A polymerization reaction was carried out in the same manner as in Example 5 except that dimethylditelluride was not added to obtain an isoprene-acrylonitrile random copolymer.
- the conversion rate of isoprene was 92%, and the conversion rate of acrylonitrile was 82%.
- Mw was 8,690, Mn was 6,980, and Mw / Mn was 1.25.
- 1 H-NMR analysis it had a double bond at the terminal at a rate of 98%.
- Example 8 The polymerization reaction was carried out in the same manner as in Example 5 except that dimethylditelluride and 1,1′-azobis (cyclohexane-1-carbonitrile) were not added and the polymerization reaction time was 72 hours. An isoprene-acrylonitrile random copolymer was obtained. As a result of gas chromatographic analysis, the conversion rate of isoprene was 75%, and the conversion rate of acrylonitrile was 63%. As a result of GPC analysis (based on polystyrene standard sample), Mw was 4,160, Mn was 3,080, and Mw / Mn was 1.35. As a result of 1 H-NMR analysis, it had a double bond at the terminal at a rate of 97%.
- Example 9 In a nitrogen-substituted glove box, in a 30 mL glass reaction vessel, 2.56 g (20 mmol) of n-butyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd., the same shall apply hereinafter), 3-methylterranyl-1 obtained in Example 1 -36.7 mg (0.20 mmol) of propene, 16.4 mg (0.10 mmol) of azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd., the same shall apply hereinafter), 0.24 g of mesitylene as an internal standard, The mixture was stirred at 60 ° C. for 1 hour to conduct a polymerization reaction.
- n-butyl acrylate manufactured by Wako Pure Chemical Industries, Ltd., the same shall apply hereinafter
- 3-methylterranyl-1 obtained in Example 1 -36.7 mg (0.20 mmol) of propene, 16.4 mg (0.10 mmol) of azobisis
- the obtained polymerization reaction product was purified by distilling off volatile components under reduced pressure, and the purified product was dried to obtain an n-butyl acrylate polymer.
- gas chromatographic analysis the conversion of n-butyl acrylate was 91%.
- GPC analysis based on polystyrene standard sample
- Mw was 18,970
- Mn was 15,240
- Mw / Mn was 1.25.
- 1 H-NMR analysis it had a double bond at the terminal at a ratio of 90%.
- Example 10 In a glove box substituted with nitrogen, in a 30 mL glass reaction vessel, 2.56 g (20 mmol) of n-butyl acrylate, 36.7 mg (0.20 mmol) of 3-methylterranyl-1-propene obtained in Example 1, 16.4 mg (0.10 mmol) of azobisisobutyronitrile and 0.24 g of mesitylene were added as an internal standard, and these were stirred at 60 ° C. for 1 hour to carry out a polymerization reaction.
- Mw was 50,900
- Mn was 29,600
- Mw / Mn was 1.71.
- 1 H-NMR analysis it had a double bond at the terminal at a rate of 88%.
- Example 11 A styrene polymer was obtained by conducting a polymerization reaction in the same manner as in Example 9 except that 2.08 g (20 mmol) of styrene (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter the same) was used instead of n-butyl acrylate. It was. As a result of gas chromatographic analysis, the conversion of styrene was 91%. As a result of GPC analysis (based on polystyrene standard sample), Mw was 10,860, Mn was 8,150, and Mw / Mn was 1.33. As a result of 1 H-NMR analysis, it had a double bond at the terminal at a rate of 97%.
- Example 12 In a nitrogen-substituted glove box, in a 30 mL glass reaction vessel, 2.08 g (20 mmol) of styrene, 36.7 mg (0.20 mmol) of 3-methylterranyl-1-propene obtained in Example 1, azobisisobutyrate 16.4 mg (0.10 mmol) of ronitrile and 0.24 g of mesitylene were added as an internal standard, and these were stirred at 60 ° C. for 1 hour to carry out a polymerization reaction. Next, 1.00 g (10 mmol) of methyl methacrylate and 28.5 mg (0.1 mmol) of dimethylditelluride obtained in Synthesis Example 1 were added to this reaction vessel, and these were stirred at 80 ° C.
- Example 13 A polymerization reaction was carried out in the same manner as in Example 5 except that 1.00 g (10 mmol) of methyl methacrylate was used instead of acrylonitrile to obtain an isoprene-methyl methacrylate random copolymer.
- 1.00 g (10 mmol) of methyl methacrylate was used instead of acrylonitrile to obtain an isoprene-methyl methacrylate random copolymer.
- the conversion rate of isoprene was 97%
- the conversion rate of methyl methacrylate was 90%.
- Mw was 9,110
- Mn was 7,530
- Mw / Mn 1.21.
- 1 H-NMR analysis it had double bonds at the terminals at a ratio of 96%.
- Example 14 A polymerization reaction was carried out in the same manner as in Example 5 except that 1.28 g (10 mmol) of n-butyl acrylate was used instead of acrylonitrile to obtain an isoprene-n-butyl acrylate random copolymer.
- the conversion rate of isoprene was 99%, and the conversion rate of n-butyl acrylate was 87%.
- Mw was 5,800, Mn was 4,700, and Mw / Mn was 1.23.
- 1 H-NMR analysis it had a double bond at the terminal at a ratio of 95%.
- Example 15 A polymerization reaction was carried out in the same manner as in Example 5 except that 1.04 g (10 mmol) of styrene was used instead of acrylonitrile to obtain an isoprene-styrene random copolymer.
- the conversion rate of isoprene was 93%, and the conversion rate of styrene was 73%.
- Mw was 8,070, Mn was 6,580, and Mw / Mn was 1.19.
- 1 H-NMR analysis it had a double bond at the terminal at a rate of 98%.
- Example 16 In a nitrogen-substituted glove box, in a 30 mL stainless steel autoclave, 1.62-g (30 mmol) of 1,3-butadiene (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.59 g (30 mmol) of acrylonitrile, 3- Methylterranyl-1-propene 0.6 mg (0.003 mmol), dimethylditelluride 0.1 mg (0.0006 mmol), 1,1′-azobis (cyclohexane-1-carbonitrile) 1.5 mg (0.009 mmol), As an internal standard, 0.24 g of mesitylene was added, and these were stirred at 80 ° C. for 21 hours to carry out a polymerization reaction.
- 1,3-butadiene manufactured by Tokyo Chemical Industry Co., Ltd.
- Methylterranyl-1-propene 0.6 mg (0.003 mmol)
- dimethylditelluride 0.1 mg 0.0006 mmol
- the resulting polymerization reaction product was purified by distilling off the volatile components under reduced pressure, and the purified product was dried to obtain a butadiene-acrylonitrile random copolymer.
- gas chromatographic analysis the conversion of 1,3-butadiene was 81%, and the conversion of acrylonitrile was 58%.
- GPC analysis based on polystyrene standard sample
- Mw was 332,300
- Mn was 223,000
- Mw / Mn was 1.49.
- 1 H-NMR analysis it had double bonds at the terminals at a ratio of 96%.
- Example 17 In a nitrogen-substituted glove box, in a 30 mL glass reaction vessel, cis-1,3-pentadiene (Tokyo Chemical Industry Co., Ltd.) 0.68 g (10 mmol), acrylonitrile 0.53 g (10 mmol), obtained in Example 1 3-methylterranyl-1-propene 1.2 mg (0.0067 mmol), dimethylditelluride 0.4 mg (0.0013 mmol), 1,1′-azobis (cyclohexane-1-carbonitrile) 0.8 mg (0. 003 mmol), 0.24 g of mesitylene was added as an internal standard, and these were stirred at 80 ° C. for 38 hours to carry out a polymerization reaction.
- cis-1,3-pentadiene Tokyo Chemical Industry Co., Ltd.
- the resulting polymerization reaction product was purified by distilling off the volatile components under reduced pressure, and the purified product was dried to obtain a cis-1,3-pentadiene-acrylonitrile random copolymer.
- gas chromatographic analysis the conversion of cis-1,3-pentadiene was 76%, and the conversion of acrylonitrile was 36%.
- GPC analysis (based on polystyrene standard sample), Mw was 89,400, Mn was 60,400, and Mw / Mn was 1.48.
- 1 H-NMR analysis it had a double bond at the terminal at a ratio of 92%.
- Example 18 Instead of 3-methylterranyl-1-propene, 49.1 mg (0.2 mmol) of 3-phenylterranyl-1-propene obtained in Example 2 and diphenylditelluride instead of dimethylditelluride (manufactured by Aldrich) ) A polymerization reaction was carried out in the same manner as in Example 5 except that 8.2 mg (0.02 mmol) was used to obtain an isoprene-acrylonitrile random copolymer. As a result of gas chromatographic analysis, the conversion rate of isoprene was 91%, and the conversion rate of acrylonitrile was 82%.
- Example 19 instead of 3-methylterranyl-1-propene, 52.9 mg (0.2 mmol) of 3-[(n-butyl) terranyl] -1-cyclohexene obtained in Example 3 was used, and dimethylditelluride Instead, an isoprene-acrylonitrile random copolymer was obtained in the same manner as in Example 5 except that 7.5 mg (0.02 mmol) of dibutyl ditelluride obtained in Synthesis Example 2 was used. . As a result of gas chromatographic analysis, the conversion rate of isoprene was 91%, and the conversion rate of acrylonitrile was 84%.
- Example 20 The same procedure as in Example 10 was repeated except that 48.3 mg (0.2 mmol) of methyl 2- (methylterranylmethyl) acrylate obtained in Example 4 was used instead of 3-methylterranyl-1-propene.
- a polymerization reaction was performed to obtain an isoprene-acrylonitrile random copolymer.
- the conversion rate of isoprene was 86%
- the conversion rate of acrylonitrile was 76%.
- Mw polystyrene standard sample reference
- Mw was 8,190
- Mn was 5,570
- Mw / Mn was 1.47.
- 1 H-NMR analysis it had a double bond at the terminal at a ratio of 85%.
- Example 21 A polymerization reaction was carried out in the same manner as in Example 9 except that 3.14 g (20 mmol) of 2- (dimethylamino) ethyl methacrylate was used instead of n-butyl acrylate, to give 2- (dimethylamino) ethyl methacrylate. A polymer was obtained. As a result of gas chromatographic analysis, the conversion of 2- (dimethylamino) ethyl methacrylate was 83%. As a result of GPC analysis (based on polystyrene standard sample), Mw was 25,900, Mn was 19,300, and Mw / Mn was 1.34. As a result of 1 H-NMR analysis, it had a double bond at the terminal at a ratio of 87%.
- the obtained polymerization reaction product was purified by distilling off volatile components under reduced pressure, and the purified product was dried to obtain a 2- (dimethylamino) ethyl methacrylate polymer.
- the conversion of 2- (dimethylamino) ethyl methacrylate was 42%.
- Mw was 36,000
- Mn was 13,300
- Mw / Mn was 2.71.
- the distribution of the obtained polymer was relatively wide.
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Abstract
Description
例えば、特許文献1には、分子末端に、重合性の炭素-炭素二重結合を有する基を有するマクロモノマーを重合する、分岐構造を有する重合体の製造方法が開示されている。この文献には、用いるマクロモノマーの製造方法として、重合開始剤(有機ハロゲン化物等)および触媒(遷移金属錯体等)を用いる原子移動ラジカル重合法により、ビニル系モノマーを重合して、末端にハロゲン基を有するビニル系重合体を得、次いで、その末端のハロゲン基を、二重結合を有する化合物等で置換する方法等が記載されている。 Conventionally, a polymer having a double bond at a molecular end has been used as a macromonomer when producing a polymer having a branched structure such as a graft polymer or a star polymer.
For example, Patent Document 1 discloses a method for producing a polymer having a branched structure in which a macromonomer having a group having a polymerizable carbon-carbon double bond at the molecular end is polymerized. In this document, as a method for producing a macromonomer to be used, a vinyl monomer is polymerized by an atom transfer radical polymerization method using a polymerization initiator (such as an organic halide) and a catalyst (such as a transition metal complex), and a terminal is formed with a halogen. A method of obtaining a vinyl polymer having a group and then substituting the terminal halogen group with a compound having a double bond or the like is described.
しかしながら、ラジカル重合開始剤は炭素-炭素二重結合に対して反応性を有するために、多くのラジカル重合開始剤では、その分子内に炭素-炭素二重結合を導入すると、十分な重合活性を示すことができなくなるという問題があり、望まれているような炭素-炭素二重結合を有するラジカル重合開始剤は得られていない。 In the method of substituting a functional group such as a halogen group at the molecular end with a group having a carbon-carbon double bond as disclosed in Patent Document 1, it is necessary to undergo a reaction for substituting the functional group. Therefore, in order to obtain a macromonomer more easily, a method of introducing a carbon-carbon double bond at the polymerization initiation terminal using a polymerization initiator having a carbon-carbon double bond has been studied. Examples of such a method include an atom transfer radical polymerization method using allyl halide as a polymerization initiator as disclosed in Non-Patent Document 1. However, the atom transfer radical polymerization method using allyl halide as a polymerization initiator has limitations on the types of vinyl monomers that can be applied, and depending on the type of vinyl monomer, it may be difficult to control the polymerization reaction. There is a problem that it does not progress. Therefore, a radical polymerization initiator having a carbon-carbon double bond that can be applied to a wide variety of radical polymerizable monomers such as vinyl monomers and perform a controlled polymerization reaction is eagerly desired.
However, since radical polymerization initiators are reactive with carbon-carbon double bonds, many radical polymerization initiators have sufficient polymerization activity when carbon-carbon double bonds are introduced into the molecule. There is a problem that it cannot be shown, and a radical polymerization initiator having a carbon-carbon double bond as desired has not been obtained.
〔3〕重合反応系に、さらに、アゾ系ラジカル発生剤を存在させることを特徴とする〔2〕に記載の重合体の製造方法。
〔4〕重合反応系に、光を照射しながら、ラジカル重合性単量体をラジカル重合することを特徴とする〔2〕または〔3〕に記載の重合体の製造方法。
〔5〕重合反応系に、さらに、下記式(3)で示されるジテルリド化合物を存在させることを特徴とする〔2〕~〔4〕のいずれかに記載の重合体の製造方法。 [2] A method for producing a polymer, comprising radically polymerizing a radical polymerizable monomer in the presence of the radical polymerization initiator according to [1].
[3] The method for producing a polymer as described in [2], wherein an azo radical generator is further present in the polymerization reaction system.
[4] The method for producing a polymer as described in [2] or [3], wherein the polymerization reaction system is radically polymerized with a radical polymerizable monomer while irradiating light.
[5] The method for producing a polymer as described in any one of [2] to [4], wherein a ditelluride compound represented by the following formula (3) is further present in the polymerization reaction system.
〔6〕前記〔2〕~〔5〕のいずれかに記載の重合体の製造方法により得られる重合体。 (Wherein R 10 and R 11 each independently have an alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group and a substituent; Represents a group selected from aromatic heterocyclic groups which may be
[6] A polymer obtained by the method for producing a polymer according to any one of [2] to [5].
「分子末端に二重結合を有する」とは、式(1)で示される有機テルル化合物由来の、式:(R5)(R6)C=C(R4)-C(R2)(R3)-で示される基が、重合体鎖の一方の末端を構成することをいう。 According to the present invention, a radical polymerization initiator useful for the production of a polymer having a double bond at the molecular end, which can be applied to a wide variety of radical polymerizable monomers to perform a controlled polymerization reaction. And a method for producing a polymer using the radical polymerization initiator.
“Having a double bond at the molecular end” means the formula: (R 5 ) (R 6 ) C═C (R 4 ) —C (R 2 ) () derived from the organic tellurium compound represented by the formula (1) The group represented by R 3 ) — constitutes one terminal of the polymer chain.
本発明のラジカル重合開始剤は、前記式(1)で示される有機テルル化合物からなるものである。 1) Radical polymerization initiator The radical polymerization initiator of the present invention is composed of an organic tellurium compound represented by the formula (1).
本明細書において、「置換基を有していてもよい」とは、「無置換又は置換基を有する」を意味する。 In Formula (1), R 1 represents an alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, and an optionally substituted aromatic complex. The group selected from a cyclic group is represented. Among these, R 1 is preferably an alkyl group or an aryl group which may have a substituent.
In this specification, “optionally substituted” means “unsubstituted or substituted”.
R1のアルキル基としては、メチル基、エチル基、n-プロピル基、n-ブチル基、n-ペンチル基、n-ヘキシル基、n-ヘプチル基、n-オクチル基、n-ノニル基、n-デシル基等の直鎖アルキル基;イソプロピル基、sec-ブチル基、tert-ブチル基等の分岐アルキル基が挙げられる。 The number of carbon atoms of the alkyl group of R 1 is not particularly limited, but is preferably 1 to 10, more preferably 1 to 8, and further preferably 1 to 5 from the viewpoint of availability.
Examples of the alkyl group for R 1 include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n -Straight chain alkyl groups such as decyl group; branched alkyl groups such as isopropyl group, sec-butyl group and tert-butyl group.
R1の置換基を有していてもよいシクロアルキル基のシクロアルキル基としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基等が挙げられる。
R1の置換基を有していてもよいシクロアルキル基の置換基は、重合反応を妨げないものであれば特に限定されない。例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子;水酸基;メチル基、エチル基、n-プロピル基、イソプロピル基等の炭素数1~8のアルキル基;メトキシ基、エトキシ基等の炭素数1~8のアルコキシ基;アミノ基;ニトロ基;シアノ基;-CORaで示される基(Raは、メチル基、エチル基、n-プロピル基、イソプロピル基等の炭素数1~8のアルキル基;シクロプロピル基、シクロブチル基、シクロペンチル基等の炭素数3~8のシクロアルキル基;フェニル基、1-ナフチル基、2-ナフチル基等の炭素数6~10のアリール基;メトキシ基、エトキシ基等の炭素数1~8のアルコキシ基;フェノキシ基、2,4,6-トリメチルフェニルオキシ基等の置換基を有していてもよい炭素数6~10のアリーロキシ基;トリフルオロメチル基等の炭素数1~8のハロアルキル基;等が挙げられる。 The carbon number of the cycloalkyl group of the cycloalkyl group which may have a substituent for R 1 is usually 3 to 10, preferably 3 to 8, and more preferably 5 or 6, from the viewpoint of availability. preferable.
Examples of the cycloalkyl group of the cycloalkyl group which may have a substituent for R 1 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like.
The substituent of the cycloalkyl group that may have the substituent of R 1 is not particularly limited as long as it does not hinder the polymerization reaction. For example, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxyl group; alkyl group having 1 to 8 carbon atoms such as methyl group, ethyl group, n-propyl group and isopropyl group; methoxy group, ethoxy group and the like An alkoxy group having 1 to 8 carbon atoms; an amino group; a nitro group; a cyano group; a group represented by —CORa (where Ra is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, etc. An alkyl group; a cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclobutyl group and a cyclopentyl group; an aryl group having 6 to 10 carbon atoms such as a phenyl group, a 1-naphthyl group and a 2-naphthyl group; a methoxy group; An alkoxy group having 1 to 8 carbon atoms such as an ethoxy group; an ant having 6 to 10 carbon atoms which may have a substituent such as a phenoxy group or a 2,4,6-trimethylphenyloxy group; Proxy group; a haloalkyl group having 1 to 8 carbon atoms such as a trifluoromethyl group; and the like.
置換基を有していてもよいアリール基のアリール基としては、フェニル基、1-ナフチル基、2-ナフチル基、アントラニル基等が挙げられる。
置換基を有していてもよいアリール基の置換基は、重合反応を妨げないものであれば特に限定されない。例えば、置換基を有していてもよいシクロアルキル基の置換基として示したものと同様のものが挙げられる。 The carbon number of the aryl group of the aryl group which may have a substituent of R 1 is usually 6 to 20, preferably 6 to 15 and more preferably 6 to 10 from the viewpoint of availability. .
Examples of the aryl group of the aryl group which may have a substituent include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and an anthranyl group.
The substituent of the aryl group that may have a substituent is not particularly limited as long as it does not interfere with the polymerization reaction. For example, the thing similar to what was shown as a substituent of the cycloalkyl group which may have a substituent is mentioned.
置換基を有していてもよい芳香族複素環基の芳香族複素環基としては、ピロリル基、イミダゾリル基、フリル基、チエニル基、オキサゾリル基、チアゾリル基等の5員環の芳香族複素環基;ピリジル基、ピリミジル基、ピリダジル基、ピラジニル基等の6員環の芳香族複素環基;ベンズイミダゾリル基、キノリル基、ベンゾフラニル基等の縮合芳香族複素環基;等が挙げられる。
置換基を有していてもよい芳香族複素環基の置換基は、重合反応を妨げないものであれば特に限定されない。例えば、置換基を有していてもよいシクロアルキル基の置換基として示したものと同様のものが挙げられる。 The aromatic heterocyclic group of the aromatic heterocyclic group which may have a substituent for R 1 usually has 1 to 15 carbon atoms, and preferably 3 to 15 from the viewpoint of availability. 10 is more preferable.
The aromatic heterocyclic group of the aromatic heterocyclic group which may have a substituent is a 5-membered aromatic heterocyclic ring such as a pyrrolyl group, an imidazolyl group, a furyl group, a thienyl group, an oxazolyl group or a thiazolyl group. Groups; 6-membered aromatic heterocyclic groups such as pyridyl group, pyrimidyl group, pyridazyl group and pyrazinyl group; condensed aromatic heterocyclic groups such as benzimidazolyl group, quinolyl group and benzofuranyl group;
The substituent of the aromatic heterocyclic group which may have a substituent is not particularly limited as long as it does not interfere with the polymerization reaction. For example, the thing similar to what was shown as a substituent of the cycloalkyl group which may have a substituent is mentioned.
R2およびR3の脂肪族炭化水素基としては、メチル基、エチル基等の炭素数1~10のアルキル基;1-プロペニル基、2-プロペニル基等の炭素数2~10のアルケニル基;1-プロピニル基、2-プロピニル基等の炭素数2~10のアルキニル基:シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基等の炭素数3~10のシクロアルキル基;等が挙げられる。 The carbon number of the aliphatic hydrocarbon group for R 2 and R 3 is preferably 1 to 10, more preferably 1 to 8, and further preferably 1 to 5.
Examples of the aliphatic hydrocarbon group for R 2 and R 3 include an alkyl group having 1 to 10 carbon atoms such as a methyl group and an ethyl group; an alkenyl group having 2 to 10 carbon atoms such as a 1-propenyl group and a 2-propenyl group; Alkynyl groups having 2 to 10 carbon atoms such as 1-propynyl group and 2-propynyl group: cycloalkyl groups having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group;
R2およびR3の置換基を有していてもよい芳香族複素環基の具体例としては、R1の置換基を有していてもよい芳香族複素環基として示したものと同様のものが挙げられる。
R2およびR3のハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。 Specific examples of the aryl group which may have a substituent for R 2 and R 3 include the same aryl groups as those which may have a substituent for R 1 .
Specific examples of the aromatic heterocyclic group which may have a substituent of R 2 and R 3 are the same as those shown as the aromatic heterocyclic group which may have a substituent of R 1 . Things.
Examples of the halogen atom for R 2 and R 3 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
R2およびR3のヒドロカルビルオキシカルボニル基としては、メチルオキシカルボニル基、エチルオキシカルボニル基等のアルキルオキシカルボニル基;エテニルオキシカルボニル基、2-プロペニルオキシカルボニル基等のアルケニルオキシカルボニル基;プロパギルオキシカルボニル基等のアルキニルオキシカルボニル基;フェノキシカルボニル基、4-メチルフェニルオキシカルボニル基、4-クロロフェノキシカルボニル基、1-ナフチルオキシカルボニル基、2-ナフチルオキシカルボニル基等の、置換基を有していてもよいアリールオキシカルボニル基;等が挙げられる。 The carbon number of the hydrocarbyloxycarbonyl group of R 2 and R 3 is preferably 2 to 10, more preferably 2 to 8, and further preferably 2 to 5.
Examples of the hydrocarbyloxycarbonyl group for R 2 and R 3 include alkyloxycarbonyl groups such as methyloxycarbonyl group and ethyloxycarbonyl group; alkenyloxycarbonyl groups such as ethenyloxycarbonyl group and 2-propenyloxycarbonyl group; propargyl Alkynyloxycarbonyl group such as oxycarbonyl group; having a substituent such as phenoxycarbonyl group, 4-methylphenyloxycarbonyl group, 4-chlorophenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group Aryloxycarbonyl group which may be present; and the like.
R4、R5およびR6の置換基を有していてもよいアリール基の具体例としては、R1の置換基を有していてもよいアリール基として示したものと同様のものが挙げられる。
R4、R5およびR6の置換基を有していてもよい芳香族複素環基の具体例としては、R1の置換基を有していてもよい芳香族複素環基として示したものと同様のものが挙げられる。
R4、R5およびR6のハロゲン原子の具体例としては、R2およびR3のハロゲン原子として示したものと同様のものが挙げられる。
R4、R5およびR6のヒドロカルビルオキシカルボニル基の具体例としては、R2およびR3のヒドロカルビルオキシカルボニル基として示したものと同様のものが挙げられる。
R4、R5およびR6のアミド基の具体例としては、R2およびR3のアミド基として示したものと同様のものが挙げられる。 Specific examples of the aliphatic hydrocarbon group for R 4 , R 5 and R 6 include the same as those shown as the aliphatic hydrocarbon group for R 2 and R 3 .
Specific examples of the aryl group which may have a substituent for R 4 , R 5 and R 6 include the same aryl groups as those which may have a substituent for R 1. It is done.
Specific examples of the aromatic heterocyclic group which may have a substituent of R 4 , R 5 and R 6 include those shown as the aromatic heterocyclic group which may have a substituent of R 1 The same thing is mentioned.
Specific examples of the halogen atom for R 4 , R 5 and R 6 include the same as those shown for the halogen atom for R 2 and R 3 .
Specific examples of the hydrocarbyloxycarbonyl group for R 4 , R 5 and R 6 include the same as those shown as the hydrocarbyloxycarbonyl group for R 2 and R 3 .
Specific examples of the amide group for R 4 , R 5 and R 6 include the same amide groups as those for R 2 and R 3 .
環は、5~7員環が好ましく、6員環がより好ましい。
R3とR6の結合やR4とR5の結合のように、環が二重結合を有する場合、環としては、置換基を有していてもよいシクロペンテン環、置換基を有していてもよいシクロヘキセン環、置換基を有していてもよいシクロヘプテン環等が挙げられる。
R5とR6の結合のように、環が二重結合を有さない場合、環としては、置換基を有していてもよいシクロペンタン環、置換基を有していてもよいシクロヘキサン環、置換基を有していてもよいシクロヘプタン環等が挙げられる。
環に結合する置換基としては、R2~R6の置換基として示したものと同様のものが挙げられる。 In R 2 to R 6 , two groups selected from these may be bonded to form a ring other than an aromatic ring. As the ring other than the aromatic ring, a hydrocarbon ring is preferable.
The ring is preferably a 5- to 7-membered ring, more preferably a 6-membered ring.
When the ring has a double bond such as a bond between R 3 and R 6 or a bond between R 4 and R 5 , the ring may have a cyclopentene ring which may have a substituent, or a substituent. A cyclohexene ring which may be substituted, a cycloheptene ring which may have a substituent, and the like.
When the ring does not have a double bond like the bond of R 5 and R 6 , the ring may be a cyclopentane ring which may have a substituent or a cyclohexane ring which may have a substituent. And a cycloheptane ring which may have a substituent.
Examples of the substituent bonded to the ring are the same as those shown as the substituents for R 2 to R 6 .
3-メチルテラニル-1-シクロペンテン、3-メチルテラニル-1-シクロヘキセン、3-メチルテラニル-1-シクロオクテン、3-エチルテラニル-1-シクロヘキセン、3-メチルテラニル-1-シクロヘキセン、3-[(n-プロピル)テラニル]-1-シクロヘキセン、3-[(n-ブチル)テラニル]-1-シクロヘキセン、
2-(メチルテラニルメチル)アクリル酸メチル、2-(メチルテラニルメチル)アクリル酸エチル、2-(メチルテラニルメチル)アクリル酸n-ブチル、2-(エチルテラニルメチル)アクリル酸メチル、2-[(n-ブチル)テラニルメチル]アクリル酸メチル、2-(シクロヘキシルテラニルメチル)アクリル酸メチル、
1,4-ビス(メチルテラニル)-2-ブテン、1,4-ビス(エチルテラニル)-2-ブテン、1,4-ビス[(n-ブチル)テラニル]-2-ブテン、1,4-ビス(シクロヘキシルテラニル)-2-ブテン、1,4-ビス(フェニルテラニル)-2-ブテン等が挙げられる。本発明で用いられる有機テルル化合物はこれらに限定されるものではない。 Specific examples of the organic tellurium compound represented by the formula (1) include 3-methylterranyl-1-propene, 3-methylterranyl-2-methyl-1-propene, 3-methylterranyl-2-phenyl-1-propene, 3- Methyl terranyl-3-methyl-1-propene, 3-methyl terranyl-3-phenyl-1-propene, 3-methyl terranyl-3-cyclohexyl-1-propene, 3-methyl terranyl-3-cyano-1-propene, 3-ethyl terranyl- 1-propene, 3-methylteranyl-3-dimethylaminocarbonyl-1-propene, 3-[(n-propyl) terranyl] -1-propene, 3-isopropylterranyl-1-propene, 3- (n-butyl) Terranylpropene, 3-[(n-hexyl) terranyl] -1-propene, 3-phenylterranyl- -Propene, 3-[(p-methylphenyl) terranyl] -1-propene, 3-cyclohexyl terranyl-1-propene, 3-[(2-pyridyl) terranyl] -1-propene, 3-methyl terranyl-2- Butene,
3-methyl terranyl-1-cyclopentene, 3-methyl terranyl-1-cyclohexene, 3-methyl terranyl-1-cyclooctene, 3-ethyl terranyl-1-cyclohexene, 3-methyl terranyl-1-cyclohexene, 3-[(n-propyl) terranyl ] -1-cyclohexene, 3-[(n-butyl) terranyl] -1-cyclohexene,
2- (methyl teranylmethyl) methyl acrylate, 2- (methyl terranyl methyl) ethyl acrylate, 2- (methyl terranyl methyl) acrylate n-butyl, 2- (ethyl teranylmethyl) methyl acrylate, 2-[(n-butyl) terranylmethyl] methyl acrylate, 2- (cyclohexyl terranylmethyl) methyl acrylate,
1,4-bis (methylterranyl) -2-butene, 1,4-bis (ethylterranyl) -2-butene, 1,4-bis [(n-butyl) terranyl] -2-butene, 1,4-bis ( Cyclohexyl teranyl) -2-butene, 1,4-bis (phenyl terranyl) -2-butene, and the like. The organic tellurium compound used in the present invention is not limited to these.
式(5)中、R1は、上記と同じものを表す。Mは、リチウム、ナトリウム、カリウムなどのアルカリ金属;マグネシウム、カルシウムなどのアルカリ土類金属;または銅;を表す。Mがアルカリ金属のとき、mは1、Mがアルカリ土類金属のとき、mは2、Mが銅のとき、mは1または2である。なお、式(5)において、Mがマグネシウムである場合は、R1で表される2つの基のうちの1つは、ハロゲン原子であってもよい。すなわち、式(5)で示される化合物は、いわゆるグリニヤール試薬であってもよい。 In the formula (4), R 2 to R 6 represent the same as described above. X represents a halogen atom. The halogen atom represented by X may be any of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, but is preferably a chlorine atom or a bromine atom.
In formula (5), R 1 represents the same as described above. M represents an alkali metal such as lithium, sodium or potassium; an alkaline earth metal such as magnesium or calcium; or copper. When M is an alkali metal, m is 1, when M is an alkaline earth metal, m is 2, and when M is copper, m is 1 or 2. In Formula (5), when M is magnesium, one of the two groups represented by R 1 may be a halogen atom. That is, the compound represented by the formula (5) may be a so-called Grignard reagent.
式(4)で示される化合物の使用量は、金属テルル1molに対して、通常、0.5~1.5mol、好ましくは0.8~1.2molである。 The amount of the compound represented by the formula (5) to be used is usually 0.5 to 1.5 mol, preferably 0.8 to 1.2 mol, relative to 1 mol of metal tellurium.
The amount of the compound represented by the formula (4) to be used is usually 0.5 to 1.5 mol, preferably 0.8 to 1.2 mol, relative to 1 mol of metal tellurium.
用いる溶媒としては、ジエチルエーテル、テトラヒドロフラン等のエーテル系溶媒;ジメチルホルムアミド等のアミド系溶媒;トルエン等の芳香族系溶媒;ヘキサン等の脂肪族炭化水素系溶媒;等が挙げられる。
式(5)で示される化合物および式(4)で示される化合物を、それぞれ反応系に加える際は、低温下(-20℃~5℃)で滴下することが好ましい。
反応条件は、特に限定されない。例えば、反応時間が5分~24時間、反応温度が-20℃~80℃である。 Examples of the inert gas include nitrogen gas, helium gas, and argon gas.
Examples of the solvent to be used include ether solvents such as diethyl ether and tetrahydrofuran; amide solvents such as dimethylformamide; aromatic solvents such as toluene; aliphatic hydrocarbon solvents such as hexane;
When the compound represented by the formula (5) and the compound represented by the formula (4) are respectively added to the reaction system, it is preferably added dropwise at a low temperature (−20 ° C. to 5 ° C.).
The reaction conditions are not particularly limited. For example, the reaction time is 5 minutes to 24 hours, and the reaction temperature is −20 ° C. to 80 ° C.
で示される化合物を用いて、同様の反応を行うことで得ることができる。 (Wherein R 2 to R 9 are the same as those described above, provided that R 4 , R 5 and R 6 are not groups represented by the formula (2). X 1 and X 2 are halogen atoms. (Preferably represents a chlorine atom or a bromine atom.)
It can obtain by performing the same reaction using the compound shown by these.
後述するように、式(1)で示される有機テルル化合物の存在下に、ラジカル重合性単量体をラジカル重合することで、重合開始末端にその炭素-炭素二重結合が導入され、しかも、制御性に優れたリビングラジカル重合反応を行うことができる。
したがって、本発明のラジカル重合開始剤を用いることで、分子末端に二重結合を有する重合体を効率よく製造することができる。 The organic tellurium compound represented by the formula (1) used as the radical polymerization initiator of the present invention has at least one non-aromatic carbon-carbon double bond at the β position with respect to Te.
As will be described later, by radical polymerization of a radical polymerizable monomer in the presence of the organic tellurium compound represented by the formula (1), the carbon-carbon double bond is introduced at the polymerization initiation terminal, A living radical polymerization reaction excellent in controllability can be performed.
Therefore, a polymer having a double bond at the molecular end can be efficiently produced by using the radical polymerization initiator of the present invention.
本発明の重合体の製造方法は、本発明のラジカル重合開始剤の存在下に、ラジカル重合性単量体をラジカル重合することを特徴とするものである。 2) Polymer Production Method The polymer production method of the present invention is characterized by radical polymerization of a radical polymerizable monomer in the presence of the radical polymerization initiator of the present invention.
エチレン、プロペン、1-ブテン、1-ペンテン、1-ヘキセン、1-オクテン、1-デセン等のα-オレフィン系単量体; Styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-methoxystyrene, 4-tert-butylstyrene, 4-n-butylstyrene, 4-tert-butoxystyrene, 2- Styrene such as hydroxymethylstyrene, 2-chlorostyrene, 4-chlorostyrene, 2,4-dichlorostyrene, 1-vinylnaphthalene, divinylbenzene, 4-styrenesulfonic acid or alkali metal salts thereof (sodium salt, potassium salt, etc.) System monomers;
Α-olefin monomers such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-decene;
1,3-ブタジエン、イソプレン、2,3-ジメチル-1,3-ブタジエン、2-クロロ-1,3-ブタジエン、1,3-ペンタジエン等の共役ジエン系単量体;
4-メチル-1,4-ヘキサジエン、7-メチル-1,6-オクタジエン等の非共役ジエン系単量体;等が挙げられる。 Unsaturated carboxylic monomers such as maleic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, maleic anhydride;
Conjugated diene monomers such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1,3-pentadiene;
And non-conjugated diene monomers such as 4-methyl-1,4-hexadiene and 7-methyl-1,6-octadiene.
これらの溶媒は、一種を単独で、あるいは二種以上を組み合わせて用いることができる。
溶媒を用いる場合、その使用量は、ラジカル重合性単量体1gに対して、例えば0.01~50ml、好ましくは、0.05~10ml、より好ましくは、0.1~5mlである。 As a solvent to be used, a solvent generally used in radical polymerization reaction can be used. For example, aromatic hydrocarbons such as benzene and toluene; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate; ethers such as dioxane and tetrahydrofuran (THF); N, N-dimethylformamide (DMF) and the like Amides; sulfur-containing compounds such as dimethyl sulfoxide (DMSO); alcohols such as methanol, ethanol, isopropanol and n-butanol; halogen-containing compounds such as chloroform, carbon tetrachloride and trifluoromethylbenzene; ethyl cellosolve and butyl cellosolve And cellosolves such as 1-methoxy-2-propanol; water; and the like.
These solvents can be used singly or in combination of two or more.
When a solvent is used, the amount used is, for example, 0.01 to 50 ml, preferably 0.05 to 10 ml, more preferably 0.1 to 5 ml with respect to 1 g of the radical polymerizable monomer.
反応は、通常、常圧下で行われるが、加圧下または減圧下で行ってもよい。 What is necessary is just to adjust reaction temperature and reaction time suitably. Usually, it is 20 to 150 ° C. for 1 minute to 100 hours, preferably 40 to 100 ° C. for 0.1 to 30 hours.
The reaction is usually performed under normal pressure, but may be performed under pressure or under reduced pressure.
アゾ系ラジカル発生剤の存在下で重合反応を行うことで、重合反応がより促進され、重合体を効率よく得ることができる。 In the polymer production method of the present invention, an azo radical generator may be further present in the polymerization reaction system.
By performing the polymerization reaction in the presence of an azo radical generator, the polymerization reaction is further promoted, and the polymer can be obtained efficiently.
例えば2,2’-アゾビス(イソブチロニトリル)(AIBN)、2,2’-アゾビス(2-メチルブチロニトリル)(AMBN)、2,2’-アゾビス(2,4-ジメチルバレロニトリル)(ADVN)、1,1’-アゾビス(シクロヘキサン-1-カルボニトリル)(ACHN)、ジメチル-2,2’-アゾビスイソブチレート(MAIB)、4,4’-アゾビス(4-シアノバレリアン酸)(ACVA)、1,1’-アゾビス(1-アセトキシ-1-フェニルエタン)、2,2’-アゾビス(2-メチルブチルアミド)、2,2’-アゾビス(4-メトキシ-2,4-ジメチルバレロニトリル)、2,2’-アゾビス(2-メチルアミジノプロパン)二塩酸塩、2,2’-アゾビス[2-(2-イミダゾリン-2-イル)プロパン]、2,2’-アゾビス[2-メチル-N-(2-ヒドロキシエチル)プロピオンアミド]、2,2’-アゾビス(2,4,4-トリメチルペンタン)、2-シアノ-2-プロピルアゾホルムアミド、2,2’-アゾビス(N-ブチル-2-メチルプロピオンアミド)、2,2’-アゾビス(N-シクロヘキシル-2-メチルプロピオンアミド)等が挙げられる。
これらのアゾ系ラジカル発生剤は、一種を単独で、あるいは二種以上を組み合わせて用いることができる。 The azo radical generator can be used without particular limitation as long as it is an azo radical generator used as a polymerization initiator or polymerization accelerator in ordinary radical polymerization.
For example, 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis (2-methylbutyronitrile) (AMBN), 2,2′-azobis (2,4-dimethylvaleronitrile) (ADVN), 1,1′-azobis (cyclohexane-1-carbonitrile) (ACHN), dimethyl-2,2′-azobisisobutyrate (MAIB), 4,4′-azobis (4-cyanovaleric acid ) (ACVA), 1,1′-azobis (1-acetoxy-1-phenylethane), 2,2′-azobis (2-methylbutyramide), 2,2′-azobis (4-methoxy-2,4) -Dimethylvaleronitrile), 2,2'-azobis (2-methylamidinopropane) dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobi [2-Methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis (2,4,4-trimethylpentane), 2-cyano-2-propylazoformamide, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (N-cyclohexyl-2-methylpropionamide) and the like.
These azo radical generators can be used singly or in combination of two or more.
例えば低温(40℃以下)で重合反応を行う場合は、2,2’-アゾビス(2,4-ジメチルバレロニトリル)(ADVN)、2,2’-アゾビス(4-メトキシ-2,4-ジメチルバレロニトリル)が好ましく、中温(40~80℃)で重合反応を行う場合は、2,2’-アゾビス(イソブチロニトリル)(AIBN)、2,2’-アゾビス(2-メチルブチロニトリル)(AMBN)、ジメチル-2,2’-アゾビスイソブチレート(MAIB)、1,1’-アゾビス(1-アセトキシ-1-フェニルエタン)が好ましく、高温(80℃以上)で重合反応を行う場合は、1,1’-アゾビス(シクロヘキサン-1-カルボニトリル)(ACHN)、2-シアノ-2-プロピルアゾホルムアミド、2,2’-アゾビス(N-ブチル-2-メチルプロピオンアミド)、2,2’-アゾビス(N-シクロヘキシル-2-メチルプロピオンアミド)、2,2’-アゾビス(2,4,4-トリメチルペンタン)が好ましい。 These azo radical generators are preferably selected as appropriate according to the reaction conditions.
For example, when the polymerization reaction is performed at a low temperature (40 ° C. or lower), 2,2′-azobis (2,4-dimethylvaleronitrile) (ADVN), 2,2′-azobis (4-methoxy-2,4-dimethyl) Valeronitrile) is preferred, and when the polymerization reaction is carried out at an intermediate temperature (40 to 80 ° C.), 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis (2-methylbutyronitrile) ) (AMBN), dimethyl-2,2′-azobisisobutyrate (MAIB), 1,1′-azobis (1-acetoxy-1-phenylethane) are preferred, and the polymerization reaction is carried out at a high temperature (80 ° C. or higher). When performing, 1,1′-azobis (cyclohexane-1-carbonitrile) (ACHN), 2-cyano-2-propylazoformamide, 2,2′-azobis (N-butyl-2-methylpropylene) N'amido), 2,2'-azobis (N- cyclohexyl-2-methylpropionamide), 2,2'-azobis (2,4,4-trimethylpentane) are preferred.
重合反応系に光を照射しながら重合反応を行うことで、重合反応がより促進され、重合体を効率よく得ることができる。
照射する光としては、紫外線(波長200~380nmの光)または可視光(波長380~830nmの光)が好ましい。光の照射は、光重合反応において通常用いられる方法により行うことができ、例えば、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、ケミカルランプ、ブラックライトランプ、マイクロウェーブ励起水銀灯、メタルハライドランプ、キセノンランプ、クリプトンランプ、LEDランプなどの光源を用いて光を照射すればよい。
なお、アゾ系ラジカル発生剤の使用および光の照射は、両者を併用することもできるが、通常はどちらか一方を行えば、十分に重合反応が促進される。 In the method for producing a polymer of the present invention, the polymerization reaction may be performed while irradiating the polymerization reaction system with light.
By conducting the polymerization reaction while irradiating the polymerization reaction system with light, the polymerization reaction is further promoted, and the polymer can be obtained efficiently.
The irradiation light is preferably ultraviolet light (light having a wavelength of 200 to 380 nm) or visible light (light having a wavelength of 380 to 830 nm). The light irradiation can be carried out by a method usually used in a photopolymerization reaction. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, a black light lamp, a microwave excited mercury lamp, a metal halide lamp, Light may be irradiated using a light source such as a xenon lamp, a krypton lamp, or an LED lamp.
The use of an azo radical generator and the irradiation of light can be used in combination, but usually the polymerization reaction is sufficiently accelerated if either one is performed.
前記式(3)で示されるジテルリド化合物の存在下で重合反応を行うことで、重合反応がより良好に制御され、より理論値に近い分子量と狭い分子量分布とを有する重合体を得ることができる。 In the method for producing a polymer of the present invention, a ditelluride compound represented by the formula (3) may further be present in the polymerization reaction system.
By performing the polymerization reaction in the presence of the ditelluride compound represented by the formula (3), the polymerization reaction is better controlled, and a polymer having a molecular weight closer to the theoretical value and a narrow molecular weight distribution can be obtained. .
R10およびR11のアルキル基、置換基を有していてもよいシクロアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよい芳香族複素環基の具体例としては、それぞれ、R1のアルキル基、置換基を有していてもよいシクロアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよい芳香族複素環基として示したものと同様のものが挙げられる。 In formula (3), R 10 and R 11 each independently have an alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group and a substituent. Represents a group selected from aromatic heterocyclic groups which may be present.
Specific examples of the alkyl group of R 10 and R 11, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, and an aromatic heterocyclic group which may have a substituent Examples include an alkyl group represented by R 1 , an optionally substituted cycloalkyl group, an optionally substituted aryl group, and an optionally substituted aromatic heterocyclic ring. The thing similar to what was shown as a group is mentioned.
これらのジテルリド化合物は、一種を単独で、あるいは二種以上を組み合わせて用いることができる。 Specific examples of the ditelluride compound represented by the formula (3) include dimethylditelluride, diethylditelluride, di (n-propyl) ditelluride, diisopropylditelluride, dicyclopropylditelluride, di (n-butyl). ) Ditelluride, di (sec-butyl) ditelluride, di (tert-butyl) ditelluride, dicyclobutylditelluride, diphenylditelluride, bis (p-methoxyphenyl) ditelluride, bis (p-aminophenyl) ditelluride, bis (P-nitrophenyl) ditelluride, bis (p-cyanophenyl) ditelluride, bis (p-sulfonylphenyl) ditelluride, bis (2-naphthyl) ditelluride, 4,4′-dipyridylditelluride and the like can be mentioned.
These ditelluride compounds can be used individually by 1 type or in combination of 2 or more types.
なお、式(3)で示されるジテルリド化合物の使用は、アゾ系ラジカル発生剤の使用および光の照射のそれぞれと併用することができる。 When the ditelluride compound represented by the formula (3) is used, the amount used is, for example, 0.01 to 100 mol, preferably 0.1 to 10 mol, based on 1 mol of the organic tellurium compound represented by the formula (1). The amount is preferably 0.1 to 5 mol.
The use of the ditelluride compound represented by the formula (3) can be used in combination with the use of an azo radical generator and the irradiation with light.
例えば、二種以上のラジカル重合性単量体を同時に重合反応系に存在させることで、ランダム共重合体を得ることができる。 In the method for producing a polymer of the present invention, a copolymer can be obtained by using two or more radically polymerizable monomers.
For example, a random copolymer can be obtained by allowing two or more kinds of radically polymerizable monomers to simultaneously exist in the polymerization reaction system.
このリビング性を有する重合体鎖の成長末端が空気中に晒されると、その成長末端が水素原子や水酸基に置き換わり、成長末端は失活する。 In the production method of the polymer of the present invention, the growth terminal of the polymer chain during the polymerization reaction is a highly reactive organic tellurium moiety (R 1 -Te- or R 7 -Te-) derived from the radical polymerization initiator of the present invention. And has a living property.
When the growth terminal of the polymer chain having the living property is exposed to the air, the growth terminal is replaced with a hydrogen atom or a hydroxyl group, and the growth terminal is deactivated.
測定装置としてBRUKER社製「BRUKER-500」を用い、溶媒としてCDCl3またはd-DMSOを用いて測定した。 [The 1 H-NMR measurement]
Measurement was performed using “BRUKER-500” manufactured by BRUKER as a measuring apparatus and using CDCl 3 or d-DMSO as a solvent.
測定装置として島津製作所社製「GC2010」を用い、カラムとしてphenomenex社製「ZB-5」を用いて測定し、定量はメシチレンを用いた内部標準法に基づいて行った。 [Gas chromatograph measurement]
The measurement was performed using “GC2010” manufactured by Shimadzu Corporation and “ZB-5” manufactured by phenomenex as a column, and quantification was performed based on an internal standard method using mesitylene.
重合体の重量平均分子量(Mw)、数平均分子量(Mn)及び分子量分布(Mw/Mn)は、テトラヒドロフラン(THF)を溶出液とし、測定装置として東ソー社製「HLC-8220」を、カラムとして東ソー社製「TSK―GEL」の「G6000HHR」、「G5000HHR」、「G4000HHR」、および「G2500HHR」をこの順で連結したものを用いたゲル・パーミエーション・クロマトグラフィー(GPC)測定により、ポリスチレン換算の値として求めた。 [Gel permeation chromatograph (GPC) measurement]
The weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the polymer were measured using tetrahydrofuran (THF) as an eluent and “HLC-8220” manufactured by Tosoh Corporation as a column as a measuring device. Polystyrene conversion by gel permeation chromatography (GPC) measurement using “TSK-GEL” “G6000HHR”, “G5000HHR”, “G4000HHR”, and “G2500HHR” in this order. Was determined as the value of.
窒素雰囲気下、300mLの三口フラスコ内で、金属テルル(Aldrich社製、以下同じ)5.23g(41mmol)をTHF45mlに懸濁させた。得られた懸濁液を撹拌しながら0℃に冷却した。懸濁液の撹拌と冷却を続けながら、この懸濁液に、メチルリチウム(1.10Mジエチルエーテル溶液、関東化学社製、以下同じ)45.0ml(43.0mmol)を、10分かけて滴下した。滴下終了後、三口フラスコ内の内容物を、室温(25℃)で20分撹拌することで、金属テルルが完全に消失した反応溶液を得た。
得られた反応溶液を撹拌しながら、この反応溶液に、飽和NH4Cl水溶液30mLを加え、1時間空気中で撹拌した。有機層を分離し、水、飽和NaCl水溶液で順次洗浄した。次いで、有機層(洗浄後の反応溶液)に、無水硫酸マグネシウムを加えて乾燥後、セライトろ過した。ろ液を減圧下で濃縮し、次いで、濃縮物を減圧蒸留(0.6mmHg、43℃)することにより、褐色油状物として、ジメチルジテルリド2.48g(収率42%)を得た。
得られたジメチルジテルリドの1H-NMRデータを以下に示す。
1H-NMR(500MHz,CDCl3,TMS,δppm)2.67(s,6H) [Synthesis Example 1]
Under a nitrogen atmosphere, 5.23 g (41 mmol) of metal tellurium (manufactured by Aldrich, the same applies hereinafter) was suspended in 45 ml of THF in a 300 mL three-necked flask. The resulting suspension was cooled to 0 ° C. with stirring. While continuing to stir and cool the suspension, 45.0 ml (43.0 mmol) of methyllithium (1.10 M diethyl ether solution, manufactured by Kanto Chemical Co., Inc., the same shall apply hereinafter) was added dropwise over 10 minutes. did. After completion of dropping, the contents in the three-necked flask were stirred at room temperature (25 ° C.) for 20 minutes to obtain a reaction solution in which metal tellurium completely disappeared.
While stirring the obtained reaction solution, 30 mL of a saturated aqueous NH 4 Cl solution was added to the reaction solution, and the mixture was stirred in the air for 1 hour. The organic layer was separated and washed successively with water and saturated aqueous NaCl. Then, anhydrous magnesium sulfate was added to the organic layer (washed reaction solution), dried, and filtered through Celite. The filtrate was concentrated under reduced pressure, and then the concentrate was distilled under reduced pressure (0.6 mmHg, 43 ° C.) to obtain 2.48 g (yield 42%) of dimethylditelluride as a brown oil.
The 1 H-NMR data of the obtained dimethylditelluride is shown below.
1 H-NMR (500 MHz, CDCl 3 , TMS, δ ppm) 2.67 (s, 6H)
窒素雰囲気下、300mLの三口フラスコ内で、金属テルル8.75g(68.6mmol)をTHF90mlに懸濁させた。得られた懸濁液を撹拌しながら0℃に冷却した。懸濁液の撹拌と冷却を続けながら、この懸濁液に、n-ブチルリチウム(1.6Mヘキサン溶液、関東化学社製、以下同じ)45.0ml(72.0mmol)を、10分かけて滴下した。滴下終了後、三口フラスコ内の内容物を、室温(25℃)で20分撹拌することで、金属テルルが完全に消失した反応溶液を得た。
得られた反応溶液を撹拌しながら、この反応溶液に、飽和NH4Cl水溶液50mLを加え、1時間空気中で撹拌した。有機層を分離し、水、飽和NaCl水溶液で順次洗浄した。次いで、有機層(洗浄後の反応溶液)に、無水硫酸マグネシウムを加えて乾燥後、セライトろ過した。ろ液を減圧下で濃縮し、次いで、濃縮物を減圧蒸留(0.2mmHg、84℃)することにより、褐色油状物として、ジブチルジテルリド4.98g(収率39%)を得た。
得られたジブチルジテルリドの1H-NMRデータを以下に示す。
1H-NMR(500MHz,CDCl3,TMS,δppm)0.93(t,J=7.4Hz、3H)、1.35-1.43(m,4H)、1.67-1.74(m,4H)、3.11(t、J=7.4Hz、4H) [Synthesis Example 2]
Under a nitrogen atmosphere, 8.75 g (68.6 mmol) of metal tellurium was suspended in 90 ml of THF in a 300 mL three-necked flask. The resulting suspension was cooled to 0 ° C. with stirring. While continuing to stir and cool the suspension, 45.0 ml (72.0 mmol) of n-butyllithium (1.6 M hexane solution, manufactured by Kanto Chemical Co., Ltd., the same shall apply hereinafter) was added to the suspension over 10 minutes. It was dripped. After completion of dropping, the contents in the three-necked flask were stirred at room temperature (25 ° C.) for 20 minutes to obtain a reaction solution in which metal tellurium completely disappeared.
While stirring the obtained reaction solution, 50 mL of a saturated aqueous NH 4 Cl solution was added to the reaction solution, and the mixture was stirred in the air for 1 hour. The organic layer was separated and washed successively with water and saturated aqueous NaCl. Then, anhydrous magnesium sulfate was added to the organic layer (washed reaction solution), dried, and filtered through Celite. The filtrate was concentrated under reduced pressure, and then the concentrate was distilled under reduced pressure (0.2 mmHg, 84 ° C.) to obtain 4.98 g (yield 39%) of dibutyl ditelluride as a brown oil.
The 1 H-NMR data of the obtained dibutyl ditelluride is shown below.
1 H-NMR (500 MHz, CDCl 3 , TMS, δ ppm) 0.93 (t, J = 7.4 Hz, 3H), 1.35 to 1.43 (m, 4H), 1.67-1.74 ( m, 4H), 3.11 (t, J = 7.4 Hz, 4H)
窒素雰囲気下、300mLの三口フラスコ内で、金属テルル11.48g(90mmol)をTHF86mlに懸濁させた。得られた懸濁液を撹拌しながら0℃に冷却した。懸濁液の撹拌と冷却を続けながら、この懸濁液に、メチルリチウム(1.10Mジエチルエーテル溶液)86.0ml(94.5mmol)を、10分かけて滴下した。滴下終了後、三口フラスコ内の内容物を、室温(25℃)で20分撹拌することで、金属テルルが完全に消失した反応溶液を得た。
得られた反応溶液を撹拌しながら0℃に冷却した。反応溶液の撹拌と冷却を続けながら、この反応溶液に、臭化アリル(東京化成工業社製、以下同じ)11.4g(94.5mmol)を加えた。そのまま、三口フラスコ内の内容物の撹拌を2時間続けて反応を行った後、反応溶液を室温に戻した。
得られた反応溶液を、脱気水、脱気飽和NH4Cl水溶液、脱気飽和NaCl水溶液で順次洗浄した。次いで、有機層(洗浄後の反応溶液)に、無水硫酸マグネシウムを加えて乾燥後、窒素雰囲気下でセライトろ過した。ろ液を減圧下で濃縮し、次いで、濃縮物を減圧蒸留(33mmHg、55℃)することにより、黄色油状物として、3-メチルテラニル-1-プロペン6.55g(収率40%)を得た。
得られた3-メチルテラニル-1-プロペンの1H-NMRデータを以下に示す。
1H-NMR(500MHz,CDCl3,TMS,δppm)1.85(s,3H),3.31(d,J=8.5Hz,2H),4.80(d,J=9.0Hz,1H),4.85(d,J=17.0Hz,1H),5.90-5.99(m,1H) [Example 1]
Under a nitrogen atmosphere, in a 300 mL three-necked flask, 11.48 g (90 mmol) of metal tellurium was suspended in 86 ml of THF. The resulting suspension was cooled to 0 ° C. with stirring. While continuing to stir and cool the suspension, 86.0 ml (94.5 mmol) of methyllithium (1.10 M diethyl ether solution) was added dropwise to the suspension over 10 minutes. After completion of dropping, the contents in the three-necked flask were stirred at room temperature (25 ° C.) for 20 minutes to obtain a reaction solution in which metal tellurium completely disappeared.
The resulting reaction solution was cooled to 0 ° C. with stirring. While continuing to stir and cool the reaction solution, 11.4 g (94.5 mmol) of allyl bromide (manufactured by Tokyo Chemical Industry Co., Ltd., the same shall apply hereinafter) was added to the reaction solution. The reaction was continued by stirring the contents in the three-necked flask for 2 hours, and the reaction solution was returned to room temperature.
The resulting reaction solution was washed successively with degassed water, degassed saturated NH 4 Cl aqueous solution, and degassed saturated NaCl aqueous solution. Subsequently, anhydrous magnesium sulfate was added to the organic layer (washed reaction solution), dried, and then filtered through Celite in a nitrogen atmosphere. The filtrate was concentrated under reduced pressure, and then the concentrate was distilled under reduced pressure (33 mmHg, 55 ° C.) to obtain 6.55 g (yield 40%) of 3-methylterranyl-1-propene as a yellow oil. .
The 1 H-NMR data of the obtained 3-methylterranyl-1-propene is shown below.
1 H-NMR (500 MHz, CDCl 3 , TMS, δ ppm) 1.85 (s, 3H), 3.31 (d, J = 8.5 Hz, 2H), 4.80 (d, J = 9.0 Hz, 1H), 4.85 (d, J = 17.0 Hz, 1H), 5.90-5.99 (m, 1H)
窒素雰囲気下、300mLの三口フラスコ内で、金属テルル6.38g(50mmol)をTHF50mlに懸濁させた。得られた懸濁液を撹拌しながら0℃に冷却した。懸濁液の撹拌と冷却を続けながら、この懸濁液に、フェニルリチウム(1.08Mシクロヘキサン・ジエチルエーテル溶液、関東化学社製)48.6ml(52.5mmol)を、10分かけて滴下した。滴下終了後、三口フラスコ内の内容物を、室温(25℃)で20分撹拌することで、金属テルルが完全に消失した反応溶液を得た。
得られた反応溶液を撹拌しながら0℃に冷却した。反応溶液の撹拌と冷却を続けながら、この反応溶液に、臭化アリル6.35g(52.5mmol)を加えた。そのまま、三口フラスコ内の内容物の撹拌を2時間続けて反応を行った後、反応溶液を室温に戻した。
得られた反応溶液を、脱気水、脱気飽和NH4Cl水溶液、脱気飽和NaCl水溶液で順次洗浄した。次いで、有機層(洗浄後の反応溶液)に、無水硫酸マグネシウムを加えて乾燥後、窒素雰囲気下でセライトろ過した。ろ液を減圧下で濃縮し、次いで、濃縮物を減圧蒸留(2.0mmHg、70℃)することにより、黄色油状物として、3-フェニルテラニル-1-プロペン5.6g(収率46%)を得た。
得られた3-フェニルテラニル-1-プロペンの1H-NMRデータを以下に示す。
1H-NMR(500MHz,CDCl3,TMS,δppm)3.63(dd,2H),4.77(d,J=10.0Hz,1H),4.83(dd,J=16.8Hz,1H),6.03-6.12(m,1H),7.18-7.78(m,5H) [Example 2]
Under a nitrogen atmosphere, 6.38 g (50 mmol) of metal tellurium was suspended in 50 ml of THF in a 300 mL three-necked flask. The resulting suspension was cooled to 0 ° C. with stirring. While continuing to stir and cool the suspension, 48.6 ml (52.5 mmol) of phenyllithium (1.08 M cyclohexane / diethyl ether solution, manufactured by Kanto Chemical Co., Inc.) was dropped into the suspension over 10 minutes. . After completion of dropping, the contents in the three-necked flask were stirred at room temperature (25 ° C.) for 20 minutes to obtain a reaction solution in which metal tellurium completely disappeared.
The resulting reaction solution was cooled to 0 ° C. with stirring. While continuing stirring and cooling of the reaction solution, 6.35 g (52.5 mmol) of allyl bromide was added to the reaction solution. The reaction was continued by stirring the contents in the three-necked flask for 2 hours, and the reaction solution was returned to room temperature.
The resulting reaction solution was washed successively with degassed water, degassed saturated NH 4 Cl aqueous solution, and degassed saturated NaCl aqueous solution. Subsequently, anhydrous magnesium sulfate was added to the organic layer (washed reaction solution), dried, and then filtered through Celite in a nitrogen atmosphere. The filtrate was concentrated under reduced pressure, and then the concentrate was distilled under reduced pressure (2.0 mmHg, 70 ° C.) to give 5.6 g of 3-phenylterranyl-1-propene (yield: 46%) as a yellow oil. )
The 1 H-NMR data of the obtained 3-phenylterranyl-1-propene is shown below.
1 H-NMR (500 MHz, CDCl 3 , TMS, δ ppm) 3.63 (dd, 2H), 4.77 (d, J = 10.0 Hz, 1H), 4.83 (dd, J = 16.8 Hz, 1H), 6.03-6.12 (m, 1H), 7.18-7.78 (m, 5H)
窒素雰囲気下、300mLの三口フラスコ内で、金属テルル3.76g(29.5mmol)をTHF38mlに懸濁させた。得られた懸濁液を撹拌しながら0℃に冷却した。懸濁液の撹拌と冷却を続けながら、この懸濁液に、n-ブチルリチウム(1.6Mヘキサン溶液)19.4ml(31.0mmol)を、10分かけて滴下した。滴下終了後、三口フラスコ内の内容物を、室温(25℃)で20分撹拌することで、金属テルルが完全に消失した反応溶液を得た。
得られた反応溶液を撹拌しながら0℃に冷却した。反応溶液の撹拌と冷却を続けながら、この反応溶液に、3-ブロモシクロヘキセン(東京化成工業社製)5.0g(31.0mmol)を加えた。そのまま、三口フラスコ内の内容物の撹拌を2時間続けて反応を行った後、反応溶液を室温に戻した。
得られた反応溶液を、脱気水、脱気飽和NH4Cl水溶液、脱気飽和NaCl水溶液で順次洗浄した。次いで、有機層(洗浄後の反応溶液)に、無水硫酸マグネシウムを加えて乾燥後、窒素雰囲気下でセライトろ過した。ろ液を減圧下で濃縮し、次いで、濃縮物を減圧蒸留(1.0mmHg、82℃)することにより、黄色油状物として、3-[(n-ブチル)テラニル]-1-シクロヘキセン4.47g(収率57%)を得た。
得られた3-[(n-ブチル)テラニル]-1-シクロヘキセンの1H-NMRデータを以下に示す。
1H-NMR(500MHz,CDCl3、TMS,δppm)0.92(t,J=7.5Hz,3H),1.38(dt,J=7.5Hz、14.8Hz,2H),1.64-1.89(m,4H)、2.01-2.22(m,4H)、2.62-2.78(m,2H)、3.96-4.00(m,1H)5.56-5.60(m,1H)、5.85-5.89(m,1H) Example 3
Under a nitrogen atmosphere, 3.76 g (29.5 mmol) of metal tellurium was suspended in 38 ml of THF in a 300 mL three-necked flask. The resulting suspension was cooled to 0 ° C. with stirring. While continuing to stir and cool the suspension, 19.4 ml (31.0 mmol) of n-butyllithium (1.6M hexane solution) was added dropwise to the suspension over 10 minutes. After completion of dropping, the contents in the three-necked flask were stirred at room temperature (25 ° C.) for 20 minutes to obtain a reaction solution in which metal tellurium completely disappeared.
The resulting reaction solution was cooled to 0 ° C. with stirring. While continuing stirring and cooling of the reaction solution, 5.0 g (31.0 mmol) of 3-bromocyclohexene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the reaction solution. The reaction was continued by stirring the contents in the three-necked flask for 2 hours, and the reaction solution was returned to room temperature.
The resulting reaction solution was washed successively with degassed water, degassed saturated NH 4 Cl aqueous solution, and degassed saturated NaCl aqueous solution. Subsequently, anhydrous magnesium sulfate was added to the organic layer (washed reaction solution), dried, and then filtered through Celite in a nitrogen atmosphere. The filtrate was concentrated under reduced pressure, and then the concentrate was distilled under reduced pressure (1.0 mmHg, 82 ° C.) to give 4.47 g of 3-[(n-butyl) terranyl] -1-cyclohexene as a yellow oil. (Yield 57%) was obtained.
1 H-NMR data of the obtained 3-[(n-butyl) terranyl] -1-cyclohexene are shown below.
1 H-NMR (500 MHz, CDCl 3 , TMS, δ ppm) 0.92 (t, J = 7.5 Hz, 3H), 1.38 (dt, J = 7.5 Hz, 14.8 Hz, 2H), 64-1.89 (m, 4H), 2.01-2.22 (m, 4H), 2.62-2.78 (m, 2H), 3.96-4.00 (m, 1H) 5 .56-5.60 (m, 1H), 5.85-5.89 (m, 1H)
窒素雰囲気下、300mLの三口フラスコ内で、金属テルル3.39g(26.6mmol)をTHF25mlに懸濁させた。得られた懸濁液を撹拌しながら0℃に冷却した。懸濁液の撹拌と冷却を続けながら、この懸濁液に、メチルリチウム(1.11Mジエチルエーテル溶液)25.1ml(27.9mmol)を、10分かけて滴下した。滴下終了後、三口フラスコ内の内容物を、室温(25℃)で20分撹拌することで、金属テルルが完全に消失した反応溶液を得た。
得られた反応溶液を撹拌しながら0℃に冷却した。反応溶液の撹拌と冷却を続けながら、この反応溶液に、2-(ブロモメチル)アクリル酸メチル(東京化成工業社製)5.0g(27.9mmol)を加えた。そのまま、三口フラスコ内の内容物の撹拌を2時間続けて反応を行った後、反応溶液を室温に戻した。
得られた反応溶液を、脱気水、脱気飽和NH4Cl水溶液、脱気飽和NaCl水溶液で順次洗浄した。次いで、有機層(洗浄後の反応溶液)に、無水硫酸マグネシウムを加えて乾燥後、窒素雰囲気下でセライトろ過した。ろ液を減圧下で濃縮し、次いで、濃縮物を減圧蒸留(1.0mmHg、52℃)することにより、黄色油状物として、2-(メチルテラニルメチル)アクリル酸メチル2.3g(収率36%)を得た。
得られた2-(メチルテラニルメチル)アクリル酸メチルの1H-NMRデータを以下に示す。
1H-NMR(500MHz,CDCl3、TMS,δppm)1.91(s,3H),3.74(s,2H),3.76(s,3H),5.54(s,1H),6.18(s,1H) Example 4
Under a nitrogen atmosphere, 3.39 g (26.6 mmol) of metal tellurium was suspended in 25 ml of THF in a 300 mL three-necked flask. The resulting suspension was cooled to 0 ° C. with stirring. While continuing to stir and cool the suspension, 25.1 ml (27.9 mmol) of methyllithium (1.11 M diethyl ether solution) was added dropwise to the suspension over 10 minutes. After completion of dropping, the contents in the three-necked flask were stirred at room temperature (25 ° C.) for 20 minutes to obtain a reaction solution in which metal tellurium completely disappeared.
The resulting reaction solution was cooled to 0 ° C. with stirring. While stirring and cooling the reaction solution, 5.0 g (27.9 mmol) of methyl 2- (bromomethyl) acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the reaction solution. The reaction was continued by stirring the contents in the three-necked flask for 2 hours, and the reaction solution was returned to room temperature.
The resulting reaction solution was washed successively with degassed water, degassed saturated NH 4 Cl aqueous solution, and degassed saturated NaCl aqueous solution. Subsequently, anhydrous magnesium sulfate was added to the organic layer (washed reaction solution), dried, and then filtered through Celite in a nitrogen atmosphere. The filtrate was concentrated under reduced pressure, and then the concentrate was distilled under reduced pressure (1.0 mmHg, 52 ° C.) to give 2.3 g of methyl 2- (methylteranylmethyl) acrylate as a yellow oil (yield 36%).
The 1 H-NMR data of the obtained methyl 2- (methylterranylmethyl) acrylate is shown below.
1 H-NMR (500 MHz, CDCl 3 , TMS, δ ppm) 1.91 (s, 3H), 3.74 (s, 2H), 3.76 (s, 3H), 5.54 (s, 1H), 6.18 (s, 1H)
窒素置換したグローブボックス内で、30mLのガラス製反応容器に、イソプレン(東京化成工業社製、以下同じ)0.68g(10mmol)、アクリロニトリル(和光純薬工業社製、以下同じ)0.53g(10mmol)、実施例1で得た3-メチルテラニル-1-プロペン36.7mg(0.20mmol)、合成例1で得たジメチルジテルリド5.7mg(0.02mmol)、1,1’-アゾビス(シクロヘキサン-1-カルボニトリル)(和光純薬工業社製、以下同じ)24.4mg(0.10mmol)、およびガスクロマトグラフ分析用内部標準(以下、「内部標準」という。)として、メシチレン(和光純薬工業社製、以下同じ)0.24gを加え、これらを80℃で16時間撹拌し、重合反応を行った。
得られた重合反応生成物を、揮発分を減圧留去することにより精製し、精製物を乾燥することにより、イソプレン-アクリロニトリルランダム共重合体を得た。
ガスクロマトグラフ分析の結果、イソプレンの転化率は93%、アクリロニトリルの転化率は84%であった。
GPC分析の結果(ポリスチレン標準サンプル基準)、重量平均分子量(Mw)は7,060、数平均分子量(Mn)は6,130、分子量分布(Mw/Mn)は1.15であった。
1H-NMR分析の結果、98%の割合で末端に二重結合を有していた。 Example 5
In a nitrogen-substituted glove box, 0.68 g (10 mmol) of isoprene (manufactured by Tokyo Chemical Industry Co., Ltd., the same shall apply hereinafter), 0.53 g of acrylonitrile (manufactured by Wako Pure Chemical Industries, Ltd., the same shall apply hereinafter) 10 mmol), 36.7 mg (0.20 mmol) of 3-methylterranyl-1-propene obtained in Example 1, 5.7 mg (0.02 mmol) of dimethylditelluride obtained in Synthesis Example 1, and 1,1′-azobis (Cyclohexane-1-carbonitrile) (manufactured by Wako Pure Chemical Industries, Ltd., the same shall apply hereinafter) 24.4 mg (0.10 mmol), and an internal standard for gas chromatographic analysis (hereinafter referred to as “internal standard”), 0.24 g was added (manufactured by Kojun Pharmaceutical Co., Ltd., the same applies hereinafter), and these were stirred at 80 ° C. for 16 hours to carry out a polymerization reaction.
The obtained polymerization reaction product was purified by distilling off volatile components under reduced pressure, and the purified product was dried to obtain an isoprene-acrylonitrile random copolymer.
As a result of gas chromatographic analysis, the conversion rate of isoprene was 93%, and the conversion rate of acrylonitrile was 84%.
As a result of GPC analysis (based on polystyrene standard sample), the weight average molecular weight (Mw) was 7,060, the number average molecular weight (Mn) was 6,130, and the molecular weight distribution (Mw / Mn) was 1.15.
As a result of 1 H-NMR analysis, it had a double bond at the terminal at a rate of 98%.
1,1’-アゾビス(シクロヘキサン-1-カルボニトリル)を添加しなかったこと、および重合反応中、重合反応系に出力6WのLEDランプ(5%NDフィルタ使用)を用いて光を照射したこと以外は、実施例5と同様にして重合反応を行い、イソプレン-アクリロニトリルランダム共重合体を得た。
ガスクロマトグラフ分析の結果、イソプレンの転化率は88%、アクリロニトリルの転化率は81%であった。
GPC分析の結果(ポリスチレン標準サンプル基準)、Mwは6,730、Mnは6,100、Mw/Mnは1.09であった。
1H-NMR分析の結果、96%の割合で末端に二重結合を有していた。 Example 6
No 1,1′-azobis (cyclohexane-1-carbonitrile) was added, and during the polymerization reaction, the polymerization reaction system was irradiated with light using a 6 W output LED lamp (using a 5% ND filter). Except for the above, a polymerization reaction was carried out in the same manner as in Example 5 to obtain an isoprene-acrylonitrile random copolymer.
As a result of gas chromatographic analysis, the conversion rate of isoprene was 88%, and the conversion rate of acrylonitrile was 81%.
As a result of GPC analysis (polystyrene standard sample reference), Mw was 6,730, Mn was 6,100, and Mw / Mn was 1.09.
As a result of 1 H-NMR analysis, it had double bonds at the terminals at a ratio of 96%.
ジメチルジテルリドを添加しなかったこと以外は、実施例5と同様にして重合反応を行い、イソプレン-アクリロニトリルランダム共重合体を得た。
ガスクロマトグラフ分析の結果、イソプレンの転化率は92%、アクリロニトリルの転化率は82%であった。
GPC分析の結果(ポリスチレン標準サンプル基準)、Mwは8,690、Mnは6,980、Mw/Mnは1.25であった。
1H-NMR分析の結果、98%の割合で末端に二重結合を有していた。 Example 7
A polymerization reaction was carried out in the same manner as in Example 5 except that dimethylditelluride was not added to obtain an isoprene-acrylonitrile random copolymer.
As a result of gas chromatographic analysis, the conversion rate of isoprene was 92%, and the conversion rate of acrylonitrile was 82%.
As a result of GPC analysis (polystyrene standard sample reference), Mw was 8,690, Mn was 6,980, and Mw / Mn was 1.25.
As a result of 1 H-NMR analysis, it had a double bond at the terminal at a rate of 98%.
ジメチルジテルリドおよび1,1’-アゾビス(シクロヘキサン-1-カルボニトリル)を添加しなかったこと、および重合反応時間を72時間にしたこと以外は、実施例5と同様にして重合反応を行い、イソプレン-アクリロニトリルランダム共重合体を得た。
ガスクロマトグラフ分析の結果、イソプレンの転化率は75%、アクリロニトリルの転化率は63%であった。
GPC分析の結果(ポリスチレン標準サンプル基準)、Mwは4,160、Mnは3,080、Mw/Mnは1.35であった。
1H-NMR分析の結果、97%の割合で末端に二重結合を有していた。 Example 8
The polymerization reaction was carried out in the same manner as in Example 5 except that dimethylditelluride and 1,1′-azobis (cyclohexane-1-carbonitrile) were not added and the polymerization reaction time was 72 hours. An isoprene-acrylonitrile random copolymer was obtained.
As a result of gas chromatographic analysis, the conversion rate of isoprene was 75%, and the conversion rate of acrylonitrile was 63%.
As a result of GPC analysis (based on polystyrene standard sample), Mw was 4,160, Mn was 3,080, and Mw / Mn was 1.35.
As a result of 1 H-NMR analysis, it had a double bond at the terminal at a rate of 97%.
窒素置換したグローブボックス内で、30mLのガラス製反応容器に、アクリル酸n-ブチル(和光純薬工業社製、以下同じ)2.56g(20mmol)、実施例1で得た3-メチルテラニル-1-プロペン36.7mg(0.20mmol)、アゾビスイソブチロニトリル(和光純薬工業社製、以下同じ)16.4mg(0.10mmol)、内部標準として、メシチレン0.24gを加え、これらを60℃で1時間撹拌し、重合反応を行った。
得られた重合反応生成物を、揮発分を減圧留去することにより精製し、精製物を乾燥することにより、アクリル酸n-ブチル重合体を得た。
ガスクロマトグラフ分析の結果、アクリル酸n-ブチルの転化率は91%であった。
GPC分析の結果(ポリスチレン標準サンプル基準)、Mwは18,970、Mnは15,240、Mw/Mnは1.25であった。
1H-NMR分析の結果、90%の割合で末端に二重結合を有していた。 Example 9
In a nitrogen-substituted glove box, in a 30 mL glass reaction vessel, 2.56 g (20 mmol) of n-butyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd., the same shall apply hereinafter), 3-methylterranyl-1 obtained in Example 1 -36.7 mg (0.20 mmol) of propene, 16.4 mg (0.10 mmol) of azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd., the same shall apply hereinafter), 0.24 g of mesitylene as an internal standard, The mixture was stirred at 60 ° C. for 1 hour to conduct a polymerization reaction.
The obtained polymerization reaction product was purified by distilling off volatile components under reduced pressure, and the purified product was dried to obtain an n-butyl acrylate polymer.
As a result of gas chromatographic analysis, the conversion of n-butyl acrylate was 91%.
As a result of GPC analysis (based on polystyrene standard sample), Mw was 18,970, Mn was 15,240, and Mw / Mn was 1.25.
As a result of 1 H-NMR analysis, it had a double bond at the terminal at a ratio of 90%.
窒素置換したグローブボックス内で、30mLのガラス製反応容器に、アクリル酸n-ブチル2.56g(20mmol)、実施例1で得た3-メチルテラニル-1-プロペン36.7mg(0.20mmol)、アゾビスイソブチロニトリル16.4mg(0.10mmol)、内部標準として、メシチレン0.24gを加え、これらを60℃で1時間撹拌し、重合反応を行った。次いで、この反応容器に、メタクリル酸メチル(和光純薬工業社製、以下同じ)1.00g(10mmol)、合成例1で得たジメチルジテルリド28.5mg(0.1mmol)を加え、これらを80℃で15時間撹拌し、重合反応を行った。
得られた重合反応生成物を、揮発分を減圧留去することにより精製し、精製物を乾燥することにより、アクリル酸n-ブチル-メタクリル酸メチルブロック共重合体を得た。
ガスクロマトグラフ分析の結果、メタクリル酸メチルの転化率は100%であった。
GPC分析の結果(ポリスチレン標準サンプル基準)、Mwは50,900、Mnは29,600、Mw/Mnは1.71であった。
1H-NMR分析の結果、88%の割合で末端に二重結合を有していた。 Example 10
In a glove box substituted with nitrogen, in a 30 mL glass reaction vessel, 2.56 g (20 mmol) of n-butyl acrylate, 36.7 mg (0.20 mmol) of 3-methylterranyl-1-propene obtained in Example 1, 16.4 mg (0.10 mmol) of azobisisobutyronitrile and 0.24 g of mesitylene were added as an internal standard, and these were stirred at 60 ° C. for 1 hour to carry out a polymerization reaction. Subsequently, 1.00 g (10 mmol) of methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd., the same shall apply hereinafter) and 28.5 mg (0.1 mmol) of dimethylditelluride obtained in Synthesis Example 1 were added to the reaction vessel. Was stirred at 80 ° C. for 15 hours to carry out a polymerization reaction.
The resulting polymerization reaction product was purified by distilling off volatile components under reduced pressure, and the purified product was dried to obtain an n-butyl acrylate-methyl methacrylate block copolymer.
As a result of gas chromatographic analysis, the conversion rate of methyl methacrylate was 100%.
As a result of GPC analysis (based on polystyrene standard sample), Mw was 50,900, Mn was 29,600, and Mw / Mn was 1.71.
As a result of 1 H-NMR analysis, it had a double bond at the terminal at a rate of 88%.
アクリル酸n-ブチルの代わりに、スチレン(東京化成工業社製、以下同じ)2.08g(20mmol)を用いたこと以外は、実施例9と同様にして重合反応を行い、スチレン重合体を得た。
ガスクロマトグラフ分析の結果、スチレンの転化率は91%であった。
GPC分析の結果(ポリスチレン標準サンプル基準)、Mwは10,860、Mnは8,150、Mw/Mnは1.33であった。
1H-NMR分析の結果、97%の割合で末端に二重結合を有していた。 Example 11
A styrene polymer was obtained by conducting a polymerization reaction in the same manner as in Example 9 except that 2.08 g (20 mmol) of styrene (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter the same) was used instead of n-butyl acrylate. It was.
As a result of gas chromatographic analysis, the conversion of styrene was 91%.
As a result of GPC analysis (based on polystyrene standard sample), Mw was 10,860, Mn was 8,150, and Mw / Mn was 1.33.
As a result of 1 H-NMR analysis, it had a double bond at the terminal at a rate of 97%.
窒素置換したグローブボックス内で、30mLのガラス製反応容器に、スチレン2.08g(20mmol)、実施例1で得た3-メチルテラニル-1-プロペン36.7mg(0.20mmol)、アゾビスイソブチロニトリル16.4mg(0.10mmol)、内部標準として、メシチレン0.24gを加え、これらを60℃で1時間撹拌し、重合反応を行った。次いで、この反応容器に、メタクリル酸メチル1.00g(10mmol)、合成例1で得たジメチルジテルリド28.5mg(0.1mmol)を加え、これらを80℃で15時間撹拌し、重合反応を行った。
得られた重合反応生成物を、揮発分を減圧留去することにより精製し、精製物を乾燥することにより、スチレン-メタクリル酸メチルブロック共重合体を得た。
ガスクロマトグラフ分析の結果、メタクリル酸メチルの転化率は100%であった。
GPC分析の結果(ポリスチレン標準サンプル基準)、Mwは26,600、Mnは18,800、Mw/Mnは1.41であった。
1H-NMR分析の結果、92%の割合で末端に二重結合を有していた。 Example 12
In a nitrogen-substituted glove box, in a 30 mL glass reaction vessel, 2.08 g (20 mmol) of styrene, 36.7 mg (0.20 mmol) of 3-methylterranyl-1-propene obtained in Example 1, azobisisobutyrate 16.4 mg (0.10 mmol) of ronitrile and 0.24 g of mesitylene were added as an internal standard, and these were stirred at 60 ° C. for 1 hour to carry out a polymerization reaction. Next, 1.00 g (10 mmol) of methyl methacrylate and 28.5 mg (0.1 mmol) of dimethylditelluride obtained in Synthesis Example 1 were added to this reaction vessel, and these were stirred at 80 ° C. for 15 hours to conduct polymerization reaction. Went.
The resulting polymerization reaction product was purified by distilling off volatile components under reduced pressure, and the purified product was dried to obtain a styrene-methyl methacrylate block copolymer.
As a result of gas chromatographic analysis, the conversion rate of methyl methacrylate was 100%.
As a result of GPC analysis (based on polystyrene standard sample), Mw was 26,600, Mn was 18,800, and Mw / Mn was 1.41.
As a result of 1 H-NMR analysis, it had a double bond at the terminal at a ratio of 92%.
アクリロニトリルの代わりに、メタクリル酸メチル1.00g(10mmol)を用いたこと以外は、実施例5と同様にして重合反応を行い、イソプレン-メタクリル酸メチルランダム共重合体を得た。
ガスクロマトグラフ分析の結果、イソプレンの転化率は97%、メタクリル酸メチルの転化率は90%であった。
GPC分析の結果(ポリスチレン標準サンプル基準)、Mwは9,110、Mnは7,530、Mw/Mn=1.21であった。
1H-NMR分析の結果、96%の割合で末端に二重結合を有していた。 Example 13
A polymerization reaction was carried out in the same manner as in Example 5 except that 1.00 g (10 mmol) of methyl methacrylate was used instead of acrylonitrile to obtain an isoprene-methyl methacrylate random copolymer.
As a result of gas chromatographic analysis, the conversion rate of isoprene was 97%, and the conversion rate of methyl methacrylate was 90%.
As a result of GPC analysis (based on polystyrene standard sample), Mw was 9,110, Mn was 7,530, and Mw / Mn = 1.21.
As a result of 1 H-NMR analysis, it had double bonds at the terminals at a ratio of 96%.
アクリロニトリルの代わりに、アクリル酸n-ブチル1.28g(10mmol)を用いたこと以外は、実施例5と同様にして重合反応を行い、イソプレン-アクリル酸n-ブチルランダム共重合体を得た。
ガスクロマトグラフ分析の結果、イソプレンの転化率は99%、アクリル酸n-ブチルの転化率は87%であった。
GPC分析の結果(ポリスチレン標準サンプル基準)、Mwは5,800、Mnは4,700、Mw/Mnは1.23であった。
1H-NMR分析の結果、95%の割合で末端に二重結合を有していた。 Example 14
A polymerization reaction was carried out in the same manner as in Example 5 except that 1.28 g (10 mmol) of n-butyl acrylate was used instead of acrylonitrile to obtain an isoprene-n-butyl acrylate random copolymer.
As a result of gas chromatographic analysis, the conversion rate of isoprene was 99%, and the conversion rate of n-butyl acrylate was 87%.
As a result of GPC analysis (based on polystyrene standard sample), Mw was 5,800, Mn was 4,700, and Mw / Mn was 1.23.
As a result of 1 H-NMR analysis, it had a double bond at the terminal at a ratio of 95%.
アクリロニトリルの代わりに、スチレン1.04g(10mmol)を用いたこと以外は、実施例5と同様にして重合反応を行い、イソプレン-スチレンランダム共重合体を得た。
ガスクロマトグラフ分析の結果、イソプレンの転化率は93%、スチレンの転化率は73%であった。
GPC分析の結果(ポリスチレン標準サンプル基準)、Mwは8,070、Mnは6,580、Mw/Mnは1.19であった。
1H-NMR分析の結果、98%の割合で末端に二重結合を有していた。 Example 15
A polymerization reaction was carried out in the same manner as in Example 5 except that 1.04 g (10 mmol) of styrene was used instead of acrylonitrile to obtain an isoprene-styrene random copolymer.
As a result of gas chromatographic analysis, the conversion rate of isoprene was 93%, and the conversion rate of styrene was 73%.
As a result of GPC analysis (polystyrene standard sample reference), Mw was 8,070, Mn was 6,580, and Mw / Mn was 1.19.
As a result of 1 H-NMR analysis, it had a double bond at the terminal at a rate of 98%.
窒素置換したグローブボックス内で、30mLのステンレス製オートクレーブに、1,3-ブタジエン(東京化成工業社製)1.62g(30mmol)、アクリロニトリル1.59g(30mmol)、実施例1で得た3-メチルテラニル-1-プロペン0.6mg(0.003mmol)、ジメチルジテルリド0.1mg(0.0006mmol)、1,1’-アゾビス(シクロヘキサン-1-カルボニトリル)1.5mg(0.009mmol)、内部標準として、メシチレン0.24gを加え、これらを80℃で21時間撹拌し、重合反応を行った。
得られた重合反応生成物を、揮発分を減圧留去することにより精製し、精製物を乾燥することにより、ブタジエン-アクリロニトリルランダム共重合体を得た。
ガスクロマトグラフ分析の結果、1,3-ブタジエンの転化率は81%、アクリロニトリルの転化率は58%であった。
GPC分析の結果(ポリスチレン標準サンプル基準)、Mwは332,300、Mnは223,000、Mw/Mnは1.49であった。
1H-NMR分析の結果、96%の割合で末端に二重結合を有していた。 Example 16
In a nitrogen-substituted glove box, in a 30 mL stainless steel autoclave, 1.62-g (30 mmol) of 1,3-butadiene (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.59 g (30 mmol) of acrylonitrile, 3- Methylterranyl-1-propene 0.6 mg (0.003 mmol), dimethylditelluride 0.1 mg (0.0006 mmol), 1,1′-azobis (cyclohexane-1-carbonitrile) 1.5 mg (0.009 mmol), As an internal standard, 0.24 g of mesitylene was added, and these were stirred at 80 ° C. for 21 hours to carry out a polymerization reaction.
The resulting polymerization reaction product was purified by distilling off the volatile components under reduced pressure, and the purified product was dried to obtain a butadiene-acrylonitrile random copolymer.
As a result of gas chromatographic analysis, the conversion of 1,3-butadiene was 81%, and the conversion of acrylonitrile was 58%.
As a result of GPC analysis (based on polystyrene standard sample), Mw was 332,300, Mn was 223,000, and Mw / Mn was 1.49.
As a result of 1 H-NMR analysis, it had double bonds at the terminals at a ratio of 96%.
窒素置換したグローブボックス内で、30mLのガラス製反応容器に、cis-1,3-ペンタジエン(東京化成工業社製)0.68g(10mmol)、アクリロニトリル0.53g(10mmol)、実施例1で得た3-メチルテラニル-1-プロペン1.2mg(0.0067mmol)、ジメチルジテルリド0.4mg(0.0013mmol)、1,1’-アゾビス(シクロヘキサン-1-カルボニトリル)0.8mg(0.003mmol)、内部標準として、メシチレン0.24gを加え、これらを80℃で38時間撹拌し、重合反応を行った。
得られた重合反応生成物を、揮発分を減圧留去することにより精製し、精製物を乾燥することにより、cis-1,3-ペンタジエン-アクリロニトリルランダム共重合体を得た。
ガスクロマトグラフ分析の結果、cis-1,3-ペンタジエンの転化率は76%、アクリロニトリルの転化率は36%であった。
GPC分析の結果(ポリスチレン標準サンプル基準)、Mwは89,400、Mnは60,400、Mw/Mnは1.48であった。
1H-NMR分析の結果、92%の割合で末端に二重結合を有していた。 Example 17
In a nitrogen-substituted glove box, in a 30 mL glass reaction vessel, cis-1,3-pentadiene (Tokyo Chemical Industry Co., Ltd.) 0.68 g (10 mmol), acrylonitrile 0.53 g (10 mmol), obtained in Example 1 3-methylterranyl-1-propene 1.2 mg (0.0067 mmol), dimethylditelluride 0.4 mg (0.0013 mmol), 1,1′-azobis (cyclohexane-1-carbonitrile) 0.8 mg (0. 003 mmol), 0.24 g of mesitylene was added as an internal standard, and these were stirred at 80 ° C. for 38 hours to carry out a polymerization reaction.
The resulting polymerization reaction product was purified by distilling off the volatile components under reduced pressure, and the purified product was dried to obtain a cis-1,3-pentadiene-acrylonitrile random copolymer.
As a result of gas chromatographic analysis, the conversion of cis-1,3-pentadiene was 76%, and the conversion of acrylonitrile was 36%.
As a result of GPC analysis (based on polystyrene standard sample), Mw was 89,400, Mn was 60,400, and Mw / Mn was 1.48.
As a result of 1 H-NMR analysis, it had a double bond at the terminal at a ratio of 92%.
3-メチルテラニル-1-プロペンの代わりに、実施例2で得た3-フェニルテラニル-1-プロペン49.1mg(0.2mmol)、ジメチルジテルリドの代わりにジフェニルジテルリド(Aldrich社製)8.2mg(0.02mmol)を用いたこと以外は、実施例5と同様にして重合反応を行い、イソプレン-アクリロニトリルランダム共重合体を得た。
ガスクロマトグラフ分析の結果、イソプレンの転化率は91%、アクリロニトリルの転化率は82%であった。
GPC分析の結果(ポリスチレン標準サンプル基準)、Mwは5,740、Mnは5,010、Mw/Mnは1.15であった。
1H-NMR分析の結果、94%の割合で末端に二重結合を有していた。 Example 18
Instead of 3-methylterranyl-1-propene, 49.1 mg (0.2 mmol) of 3-phenylterranyl-1-propene obtained in Example 2 and diphenylditelluride instead of dimethylditelluride (manufactured by Aldrich) ) A polymerization reaction was carried out in the same manner as in Example 5 except that 8.2 mg (0.02 mmol) was used to obtain an isoprene-acrylonitrile random copolymer.
As a result of gas chromatographic analysis, the conversion rate of isoprene was 91%, and the conversion rate of acrylonitrile was 82%.
As a result of GPC analysis (based on polystyrene standard sample), Mw was 5,740, Mn was 5,010, and Mw / Mn was 1.15.
As a result of 1 H-NMR analysis, it had a double bond at the terminal at a ratio of 94%.
3-メチルテラニル-1-プロペンの代わりに、実施例3で得た3-[(n-ブチル)テラニル]-1-シクロヘキセン52.9mg(0.2mmol)を用いたこと、およびジメチルジテルリドの代わりに、合成例2で得たジブチルジテルリド7.5mg(0.02mmol)を用いたこと以外は、実施例5と同様にして重合反応を行い、イソプレン-アクリロニトリルランダム共重合体を得た。
ガスクロマトグラフ分析の結果、イソプレンの転化率は91%、アクリロニトリルの転化率は84%であった。
GPC分析の結果(ポリスチレン標準サンプル基準)、Mwは7,770、Mnは6,150、Mw/Mnは1.26であった。
1H-NMR分析の結果、99%の割合で末端に二重結合を有していた。 Example 19
Instead of 3-methylterranyl-1-propene, 52.9 mg (0.2 mmol) of 3-[(n-butyl) terranyl] -1-cyclohexene obtained in Example 3 was used, and dimethylditelluride Instead, an isoprene-acrylonitrile random copolymer was obtained in the same manner as in Example 5 except that 7.5 mg (0.02 mmol) of dibutyl ditelluride obtained in Synthesis Example 2 was used. .
As a result of gas chromatographic analysis, the conversion rate of isoprene was 91%, and the conversion rate of acrylonitrile was 84%.
As a result of GPC analysis (based on polystyrene standard sample), Mw was 7,770, Mn was 6,150, and Mw / Mn was 1.26.
As a result of 1 H-NMR analysis, it had a double bond at the terminal at a ratio of 99%.
3-メチルテラニル-1-プロペンの代わりに、実施例4で得た2-(メチルテラニルメチル)アクリル酸メチル48.3mg(0.2mmol)を用いたこと以外は、実施例10と同様にして重合反応を行い、イソプレン-アクリロニトリルランダム共重合体を得た。
ガスクロマトグラフ分析の結果、イソプレンの転化率は86%、アクリロニトリルの転化率は76%であった。
GPC分析の結果(ポリスチレン標準サンプル基準)、Mwは8,190、Mnは5,570、Mw/Mnは1.47であった。
1H-NMR分析の結果、85%の割合で末端に二重結合を有していた。 Example 20
The same procedure as in Example 10 was repeated except that 48.3 mg (0.2 mmol) of methyl 2- (methylterranylmethyl) acrylate obtained in Example 4 was used instead of 3-methylterranyl-1-propene. A polymerization reaction was performed to obtain an isoprene-acrylonitrile random copolymer.
As a result of gas chromatographic analysis, the conversion rate of isoprene was 86%, and the conversion rate of acrylonitrile was 76%.
As a result of GPC analysis (polystyrene standard sample reference), Mw was 8,190, Mn was 5,570, and Mw / Mn was 1.47.
As a result of 1 H-NMR analysis, it had a double bond at the terminal at a ratio of 85%.
アクリル酸n-ブチルの代わりに、2-(ジメチルアミノ)エチルメタクリレート3.14g(20mmol)を用いたこと以外は、実施例9と同様にして重合反応を行い、2-(ジメチルアミノ)エチルメタクリレート重合体を得た。
ガスクロマトグラフ分析の結果、2-(ジメチルアミノ)エチルメタクリレートの転化率は83%であった。GPC分析の結果(ポリスチレン標準サンプル基準)、Mwは25,900、Mnは19,300、Mw/Mnは1.34であった。
1H-NMR分析の結果、87%の割合で末端に二重結合を有していた。 Example 21
A polymerization reaction was carried out in the same manner as in Example 9 except that 3.14 g (20 mmol) of 2- (dimethylamino) ethyl methacrylate was used instead of n-butyl acrylate, to give 2- (dimethylamino) ethyl methacrylate. A polymer was obtained.
As a result of gas chromatographic analysis, the conversion of 2- (dimethylamino) ethyl methacrylate was 83%. As a result of GPC analysis (based on polystyrene standard sample), Mw was 25,900, Mn was 19,300, and Mw / Mn was 1.34.
As a result of 1 H-NMR analysis, it had a double bond at the terminal at a ratio of 87%.
窒素置換したグローブボックス内で、30mLのガラス製反応容器に、臭化銅(I)(和光純薬工業社製、以下同じ)28.7mg(0.2mmol)、N,N,N’,N’’,N’’-ペンタメチルジエチレントリアミン(和光純薬工業社製)34.7mg(0.2mmol)、イソプレン0.68g(10mmol)、アクリロニトリル0.53g(10mmol)、臭化アリル24.2mg(0.20mmol)、内部標準として、メシチレン0.24gを加え、これらを80℃で15時間撹拌し、重合反応を行った。
得られた重合反応生成物を、揮発分を減圧留去することにより精製し、精製物を乾燥した。
ガスクロマトグラフ分析の結果、イソプレンの転化率は21%、アクリロニトリルの転化率は27%であった。
GPC分析の結果(ポリスチレン標準サンプル基準)、Mwは370、Mnは360、Mw/Mnは1.04であり、重合反応で得られたものはオリゴマーであった。 [Comparative Example 1]
In a glove box substituted with nitrogen, in a 30 mL glass reaction vessel, 28.7 mg (0.2 mmol) of copper (I) bromide (manufactured by Wako Pure Chemical Industries, Ltd., the same shall apply hereinafter), N, N, N ′, N '', N ''-pentamethyldiethylenetriamine (manufactured by Wako Pure Chemical Industries, Ltd.) 34.7 mg (0.2 mmol), isoprene 0.68 g (10 mmol), acrylonitrile 0.53 g (10 mmol), allyl bromide 24.2 mg ( 0.20 mmol), 0.24 g of mesitylene was added as an internal standard, and these were stirred at 80 ° C. for 15 hours to carry out a polymerization reaction.
The resulting polymerization reaction product was purified by distilling off volatile components under reduced pressure, and the purified product was dried.
As a result of gas chromatographic analysis, the conversion rate of isoprene was 21%, and the conversion rate of acrylonitrile was 27%.
As a result of GPC analysis (polystyrene standard sample reference), Mw was 370, Mn was 360, and Mw / Mn was 1.04, and what was obtained by the polymerization reaction was an oligomer.
窒素置換したグローブボックス内で、30mLのガラス製反応容器に、臭化銅(I)28.7mg(0.2mmol)、N,N,N’,N’’,N’’-ペンタメチルジエチレントリアミン34.7mg(0.2mmol)、トルエン2mL、2-(ジメチルアミノ)エチルメタクリレート3.14g(20mmol)、臭化アリル24.2mg(0.20mmol)、内部標準として、メシチレン0.24gを加え、これらを80℃で15時間撹拌し、重合反応を行った。
得られた重合反応生成物を、揮発分を減圧留去することにより精製し、精製物を乾燥することにより、2-(ジメチルアミノ)エチルメタクリレート重合体を得た。
ガスクロマトグラフ分析の結果、2-(ジメチルアミノ)エチルメタクリレートの転化率は42%であった。
GPC分析の結果(ポリスチレン標準サンプル基準)、Mwは36,000、Mnは13,300、Mw/Mnは2.71であり、得られた重合体の分布は比較的に広いものであった。 [Comparative Example 2]
In a nitrogen-substituted glove box, in a 30 mL glass reaction vessel, 28.7 mg (0.2 mmol) of copper (I) bromide, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine 34 0.7 mg (0.2 mmol), toluene 2 mL, 2- (dimethylamino) ethyl methacrylate 3.14 g (20 mmol), allyl bromide 24.2 mg (0.20 mmol), and 0.24 g of mesitylene as an internal standard were added. Was stirred at 80 ° C. for 15 hours to carry out a polymerization reaction.
The obtained polymerization reaction product was purified by distilling off volatile components under reduced pressure, and the purified product was dried to obtain a 2- (dimethylamino) ethyl methacrylate polymer.
As a result of gas chromatographic analysis, the conversion of 2- (dimethylamino) ethyl methacrylate was 42%.
As a result of GPC analysis (based on polystyrene standard sample), Mw was 36,000, Mn was 13,300, and Mw / Mn was 2.71. The distribution of the obtained polymer was relatively wide.
Claims (6)
- 下記式(1)で示される有機テルル化合物からなるラジカル重合開始剤。
R2およびR3は、それぞれ独立に、水素原子、脂肪族炭化水素基、置換基を有していてもよいアリール基、置換基を有していてもよい芳香族複素環基、ハロゲン原子、カルボキシル基、ヒドロカルビルオキシカルボニル基、シアノ基およびアミド基から選択される基を表し、
R4、R5およびR6は、それぞれ独立に、水素原子、脂肪族炭化水素基、置換基を有していてもよいアリール基、置換基を有していてもよい芳香族複素環基、ハロゲン原子、カルボキシル基、ヒドロカルビルオキシカルボニル基、シアノ基、アミド基および下記式(2)で示される基から選択される基を表す。
また、R2~R6から選択される2つの基が結合して、芳香環以外の環を形成していてもよい。)
R 2 and R 3 each independently represent a hydrogen atom, an aliphatic hydrocarbon group, an aryl group which may have a substituent, an aromatic heterocyclic group which may have a substituent, a halogen atom, Represents a group selected from a carboxyl group, a hydrocarbyloxycarbonyl group, a cyano group and an amide group,
R 4 , R 5 and R 6 are each independently a hydrogen atom, an aliphatic hydrocarbon group, an aryl group which may have a substituent, an aromatic heterocyclic group which may have a substituent, A group selected from a halogen atom, a carboxyl group, a hydrocarbyloxycarbonyl group, a cyano group, an amide group and a group represented by the following formula (2).
Two groups selected from R 2 to R 6 may be bonded to form a ring other than an aromatic ring. )
- 請求項1に記載のラジカル重合開始剤の存在下に、ラジカル重合性単量体をラジカル重合することを特徴とする重合体の製造方法。 A method for producing a polymer, comprising subjecting a radical polymerizable monomer to radical polymerization in the presence of the radical polymerization initiator according to claim 1.
- 重合反応系に、さらに、アゾ系ラジカル発生剤を存在させることを特徴とする請求項2に記載の重合体の製造方法。 3. The method for producing a polymer according to claim 2, wherein an azo radical generator is further present in the polymerization reaction system.
- 重合反応系に、光を照射しながら、ラジカル重合性単量体をラジカル重合することを特徴とする請求項2または3に記載の重合体の製造方法。 4. The method for producing a polymer according to claim 2, wherein radical polymerization of the radical polymerizable monomer is performed while irradiating the polymerization reaction system with light.
- 重合反応系に、さらに、下記式(3)で示されるジテルリド化合物を存在させることを特徴とする請求項2~4のいずれかに記載の重合体の製造方法。
- 請求項2~5のいずれかに記載の重合体の製造方法により得られる重合体。 A polymer obtained by the method for producing a polymer according to any one of claims 2 to 5.
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CN201480063079.0A CN105745230B (en) | 2013-11-27 | 2014-11-27 | The manufacturing method of radical polymerization initiator and polymer |
EP14866248.9A EP3075748B1 (en) | 2013-11-27 | 2014-11-27 | Method for producing polymers with radical polymerization initiator |
US15/038,579 US20160297755A1 (en) | 2013-11-27 | 2014-11-27 | Radical polymerization initiator and method for producing polymers |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017170250A1 (en) * | 2016-03-31 | 2017-10-05 | 日本ゼオン株式会社 | Method for producing copolymer, and method for producing latex |
WO2017191766A1 (en) * | 2016-05-02 | 2017-11-09 | 国立大学法人京都大学 | Method for producing multibranched polymer and multibranched polymer |
KR20190082663A (en) * | 2017-12-31 | 2019-07-10 | 롬 앤드 하스 일렉트로닉 머트어리얼즈 엘엘씨 | Monomers, polymers and lithographic compositions comprising same |
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EP3594250A4 (en) * | 2017-03-09 | 2021-01-13 | AGC Inc. | Method for producing polymer |
CN111848861B (en) * | 2019-04-30 | 2022-03-04 | 天津大学 | Response type hydrogel based on coordination of organic tellurium and platinum and preparation method |
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004014962A1 (en) | 2002-08-08 | 2004-02-19 | Otsuka Chemical Co., Ltd. | Process for production of living radical polymers and polymers |
JP2004323693A (en) * | 2003-04-25 | 2004-11-18 | Otsuka Chemical Co Ltd | Method for producing living radical polymer, and polymer |
JP2005344009A (en) * | 2004-06-03 | 2005-12-15 | Shin Etsu Chem Co Ltd | Polymer for resist material, method for producing the same and chemically amplified positive type resist material |
US20060052563A1 (en) | 1998-06-19 | 2006-03-09 | Kaneka Corporation | Process for producing branched polymer and polymer |
JP2007254758A (en) | 1998-06-19 | 2007-10-04 | Kaneka Corp | Process for producing branched polymer and polymer |
JP2007277533A (en) | 2006-03-11 | 2007-10-25 | Otsuka Chemical Co Ltd | Method for producing living radical polymer and polymer |
JP2012236984A (en) * | 2011-04-28 | 2012-12-06 | Kyoto Univ | Process for producing polymer, and polymer produced by the same |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5043477A (en) * | 1987-07-13 | 1991-08-27 | The United States Of America As Represented By The Secretary Of The Navy | Methyl allyl telluride |
US6274688B1 (en) * | 1997-07-28 | 2001-08-14 | Kaneka Corporation | Functional groups-terminated vinyl polymers |
DE60229446D1 (en) * | 2002-08-06 | 2008-11-27 | Otsuka Chemical Co Ltd | ORGANIC TELLUR COMPOUND, PROCESS FOR THE PRODUCTION THEREOF, INITIATOR FOR LIVING RADICAL POLYMERIZATION, METHOD FOR PRODUCING A POLYMER USING THEREOF, AND POLYMER |
US20100016191A1 (en) * | 2008-07-18 | 2010-01-21 | Harrison James J | Copolymers Made With Allyl-Terminated Polyolefins And Unsaturated Acidic Reagents, Dispersants Using Same, and Methods of Making Same |
CN102344537B (en) * | 2010-07-30 | 2014-04-16 | 奇美实业股份有限公司 | Block copolymer and polymer composition prepared with block copolymer |
-
2014
- 2014-11-27 EP EP14866248.9A patent/EP3075748B1/en active Active
- 2014-11-27 US US15/038,579 patent/US20160297755A1/en not_active Abandoned
- 2014-11-27 JP JP2015550980A patent/JP6550610B2/en active Active
- 2014-11-27 CN CN201480063079.0A patent/CN105745230B/en active Active
- 2014-11-27 WO PCT/JP2014/081334 patent/WO2015080189A1/en active Application Filing
-
2019
- 2019-06-12 US US16/439,109 patent/US10689336B2/en active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060052563A1 (en) | 1998-06-19 | 2006-03-09 | Kaneka Corporation | Process for producing branched polymer and polymer |
JP2007254758A (en) | 1998-06-19 | 2007-10-04 | Kaneka Corp | Process for producing branched polymer and polymer |
WO2004014962A1 (en) | 2002-08-08 | 2004-02-19 | Otsuka Chemical Co., Ltd. | Process for production of living radical polymers and polymers |
US20060167199A1 (en) | 2002-08-08 | 2006-07-27 | Shigeru Yamago | Process for produciton of living radical polymers and polymers |
JP2004323693A (en) * | 2003-04-25 | 2004-11-18 | Otsuka Chemical Co Ltd | Method for producing living radical polymer, and polymer |
JP2005344009A (en) * | 2004-06-03 | 2005-12-15 | Shin Etsu Chem Co Ltd | Polymer for resist material, method for producing the same and chemically amplified positive type resist material |
JP2007277533A (en) | 2006-03-11 | 2007-10-25 | Otsuka Chemical Co Ltd | Method for producing living radical polymer and polymer |
JP2012236984A (en) * | 2011-04-28 | 2012-12-06 | Kyoto Univ | Process for producing polymer, and polymer produced by the same |
Non-Patent Citations (2)
Title |
---|
See also references of EP3075748A4 * |
YOSHIKI NAKAGAWA; KRZYSZTOFMATYJASZEWSKI: "Synthesis of Well-Defined Allyl End-Functionalized Polystyrene by Atom Transfer Radical Polymerization with an Allyl Halide Initiator", POLYMER JOURNAL, vol. 30, no. 2, 1998, pages 138 - 141, XP000742712, DOI: doi:10.1295/polymj.30.138 |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017170250A1 (en) * | 2016-03-31 | 2017-10-05 | 日本ゼオン株式会社 | Method for producing copolymer, and method for producing latex |
CN108779193A (en) * | 2016-03-31 | 2018-11-09 | 日本瑞翁株式会社 | The manufacturing method of copolymer and the manufacturing method of latex |
WO2017191766A1 (en) * | 2016-05-02 | 2017-11-09 | 国立大学法人京都大学 | Method for producing multibranched polymer and multibranched polymer |
US10808065B2 (en) | 2016-05-02 | 2020-10-20 | Kyoto University | Method for producing multibranched polymer and multibranched polymer |
KR20190082663A (en) * | 2017-12-31 | 2019-07-10 | 롬 앤드 하스 일렉트로닉 머트어리얼즈 엘엘씨 | Monomers, polymers and lithographic compositions comprising same |
JP2019119851A (en) * | 2017-12-31 | 2019-07-22 | ローム アンド ハース エレクトロニック マテリアルズ エルエルシーRohm and Haas Electronic Materials LLC | Monomers, polymers and lithographic compositions comprising the same |
JP2021005115A (en) * | 2017-12-31 | 2021-01-14 | ローム アンド ハース エレクトロニック マテリアルズ エルエルシーRohm and Haas Electronic Materials LLC | Monomers, polymers and lithographic compositions comprising the same |
KR102208670B1 (en) | 2017-12-31 | 2021-01-27 | 롬 앤드 하스 일렉트로닉 머트어리얼즈 엘엘씨 | Monomers, polymers and lithographic compositions comprising same |
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EP3075748B1 (en) | 2020-11-18 |
US20160297755A1 (en) | 2016-10-13 |
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JPWO2015080189A1 (en) | 2017-03-16 |
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US20190292146A1 (en) | 2019-09-26 |
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